Method of modifying polymeric material and use thereof

ABSTRACT

A method of modifying a polymeric material whereby the polymeric material is modified to give a highly durable surface without decreasing its strength. Namely, a polymeric material is modified by the method comprising a combination of an impregnation step, an activation step, a step of grafting a monomer and a step of a treatment with a hydrophilic polymer. Thus, the hydrophilic nature, adhesiveness, and so forth of polymeric materials such as polyolefins can be improved without causing any decrease in the practical strength. The thus obtained polymeric materials are usable in articles with a need for high water absorptivity and high adhesiveness, for example, water-absorbing materials and water-retaining materials for medical, sanitary, cosmetic articles or supplies, agricultural materials, synthetic papers, filters and fiber products for clothes, for improving adhesiveness of composite materials and the like. Among all, these materials are particularly usable in dentition orthodontic appliances, writing implements and battery separators.

TECHNICAL FIELD

[0001] The present invention relates to a method of modifing theproperty of a polymeric material. More particularly, the inventionrelates to a method to improve the property of a polymeric material suchas a water absorption property, an adhesion property, and so forth,without decreasing its strength for a practical use. In addition, thepresent invention relates to the polymeric material obtained by thepresent method and its use thereof.

BACKGROUND ART

[0002] (1) Prior Art for Modification of Surface Property of PolymericMaterials

[0003] Polyolefin material, such as polypropylene and polyethylene, isexcellent in lightness, strength, chemical resistance, and so forth, andis widely used for molded goods, such as a film, a non-woven fabric, andautomobile parts, electrical machinery and apparatus parts. However, aspolyolefin materials have a low polarity and a high crystallinity, whichare derived from its chemical structure, they have a small hydrophilicproperty and a difficulty in chemical modification. Therefore, they havea low hydrophilic property and a difficulty in the chemicalmodification. Various surface activation processings such asozonization, plasma treatment, UV irradiation processing, high-pressureelectro-discharge treatment, corona discharge processing, sandblastingprocessing, solvent etching processing, chromium mixed-acid processing,and a flame treatment, and so forth have been tried in order to improvethe hydrophilic property and an adhesive property of the polyolefinmaterial. However, even if any method of the above processes is employedto treat the polyolefin material, we cannot obtain the material whichabsorbs water as much as several times of the original weight of thematerial.

[0004] For example, the method of improving plating nature, paintnature, and an adhesive property was examined by performing an ozoneoxidation treatment (JP, 3-103448,A (1991)). However, when only theozone treatment is employed to improve the property of the material,very severe reaction conditions are necessary and they cause thedecrease in the mechanical strength, which makes that the treatment isnon-practical. Furthermore, it is impossible to give a large waterabsorption property to the material only by the ozone treatment. Inorder to modify the materials by the other treatments mentioned above,the following problems are caused; the lowering in mechanical strengthof the material and the high cost for facilities and a waste disposalsystem.

[0005] In addition to the direct activation of the surface of polymericmaterials mentioned above, a method to form a layer which consists of acomponent with high reactivity on the surface of polymeric materials wasproposed. For example, it was proposed that vinyl monomers containingester groups were grafted to the nonwoven fabric of polyolefin fiber andthen, the ester groups were hydrolyzed to form acid groups which gave ahydrophilic property and an ion-exchange property (JP, 11-7937,A(1999)). However, a grafting of sufficient amount which gives a highhydrophilic property to polyolefins is not easily attained by the vinylmonomer grafting according to the proposed method. Moreover, the methodrequires the hydrolysis treatment after the grafting, which causes aproblem of taking time and effort.

[0006] On the other hand, a method to improve a hydrophilic property ofnonwoven fabrics of polyolefin fiber by the treatment with a hydrophilicresin in the presence of a persulfate was proposed (JP,11-67183,A(1999)). Although this method gave practically a hydrophilic property tothe nonwoven fabrics, the modified hydrophilic property does not give adurability in use. For instance, the hydrophilic property obtained bythis method is lost considerably by washing with a hot detergentsolution. In addition, when the materials such as films and casts otherthan a nonwoven fabric were processed, sufficient hydrophilic propertycould not be given, or the adhesive property by adhesives could not beimproved. A method to modify a hydrophilic property of nonwoven fabricsby coating polyvinyl alcohol (JP,1-248460,A (1989)) was also known.Although the hydrophilic property of the obtained material is high, ithas the problem that the durability of a hydrophilic property is notenough because the process is mere covering.

[0007] Previously, the present applicant proposed a method to improvethe surface property or especially the dyeability of polymericmaterials, which comprises an activation treatment of the surface ofpolymeric materials, a graft polymerization of monomers such as acrylamide, etc. to them or the Hofmann rearrangement of the amide groupswhich are contained in grafts (JP,8-109228,A (1997)). Although thepolymeric materials which gave the hydrophilic property on the basis ofthis method can be manufactured by this method, the kind of polymericmaterials which can be applied by the method is limited.

[0008] According to these methods, polymeric materials with a high waterabsorption property can be manufactured cheaply and easily. However,when the moldings of the polymeric materials containing additives suchas a stabilizer and an antioxidant are processed to obtain a highdurable hydrophilic property, these additives may reduce the effect ofthe activation process.

[0009] The above technical requests are desirable not only forpolyolefins but also the other polymeric materials which have moreactive surface property than polyolefins. For example, it is sometimesrequested that a surface of a polymeric material is modified to give adesirable property.

[0010] (2) Prior Art for Dentition Orthodontic Appliances

[0011] A dentition orthodontic appliance is used to correct an irregularalignment of teeth by a restitution force which is caused by an elasticsteel wire (so-called arch wire) penetrating through an appliance(so-called bracket) that is bonded to a tooth. In general, a bracket ismade of metal or ceramic. But, brackets made of polymers were producedrecently.

[0012] In the brackets made of polymeric materials, a bracket made ofpolycarbonate resin reinforced by glass fiber (a PC bracket) is atypical one, and it was disclosed in a Japanese Patent (JP, No.9-98988,A) and an U.S. Pat. No. 5254992. However, the PC bracket gives alow durability in the adhesive property to teeth and is easily pollutedwhen it is used by fitting to teeth. In addition, it was reported thatthe PC bracket produces bisphenol A which is considered to give anenvironmental pollution. Because of these problems, it is desirable toinvent a bracket made of a polymer resin which is harmless to a livingbody, is not polluted easily, and gives a strong adhesion force toteeth. As the present invention can improve the adhesive property ofpolyolefins which are known to be chemically stable, this techniqueshould be also applied to nylon and polyester, and so forth. Therefore,the present invention can provide the dentition orthodontic applianceswhich are made of ideal polymeric materials. Moreover, the dentitionorthodontic appliances mean not only brackets but also variousappliances which are useful for a dental treatment.

[0013] (3) Prior Art for Members in Writing Implements or Painting Toolsfor Stationary or Makeup.

[0014] Various members such as ink-collectors (or ink-regulators),ink-tanks, ink-guiding cores, pen cores, center rods for pens,ink-absorbing materials made of fibers, ink-retaining sponges, brushheads of brush pens, and so forth are used in writing implements. Almostof these members are generally made of polymeric materials. Because, thepolymeric material gives a high mechanical strength, an easy castingproperty, a chemical resistance, economics, and so forth. Members inwriting imprements which are used to contact to water-soluble inkrequire a wettability to water-soluble ink, an absorptivity of the inkand an ink-retaining property. In order to overcome these requirements,a development in excellent and safety skills to improve the hydrophilicproperty of synthetic polymers has been expected.

[0015] One of the typical members of writing implements is an inkcollector (which is sometimes called “a collector” in short below). Thecollector is explained in detail here. The collector is used in an inktank of a writing implement where the ink is stored directly and itplays an ink retaining body. When an expansion of the air in an ink tankis caused by a temperature increase or a lowering of the atmospherepressure, the ink pressured in the ink tank run through severallongitudinal channels on the collector surface and then it is stored inmany horizontal channels (which are called as ink-retaining channels)which are perpendicular to the longitudinal channel. Thus, the outflowof the pressured ink from air voids and nibs of pens can be avoided.When the temperature or the air pressure are recovered to the originalstate, it is necessary that the ink stored in the ink-retaining channelscomes back to the ink tank through the longitudinal channels. When awriting implement is used for a long time, a decrease in air pressure inthe ink tank is caused by a decrease in the amount of ink. As a result,when the decrease in air pressure is caused to excess, the amount of inksuitable for a good writing cannot be drawn from the nib of pens. Inorder to avoid this problem, the pressure in the ink tank must be keptat a given reduced pressure. Therefore, the ink collector has amechanism that the wasted ink is substituted with the correspondingvolume of air by the longitudinal channels in the ink tank. When awriting implement is equipped with an ink tank with an excellentcollector whose structure is preferable for storing ink directly, we canuse it with a constant amount of ink from the first writing to the finalwriting.

[0016] In addition, a writing implement with a collector made ofsynthetic resin has the following advantages. It gives a goodconsumption of ink as compared with the collector containing an inkabsorber made of fibers; we can use the ink stored in the collectoralmost completely without leaving it in the ink tank. We can see theamount of ink easily through an ink tank which is made of a transparentpolymer resin.

[0017] Therefore, a collector is an indispensable member for a writingimplement with an ink tank. However, when an ink collector surface hasan insufficient wettability to ink, the ink pressured in the ink tankcannot run smoothly into the ink-retaining channels of the collector andthe retention power of the collector to the ink is too weak to keep theink in the collector, without a capillary attraction. As a result, theink contained in the collector goes out of the ink-retaining channelseasily and the ink outflows from the air voids.

[0018] At present, an ABS resin (a three-components copolymer ofacrylonitrile, butadiene and styrene) is generally used as a materialfor the collector, because of the strength, the casting property, thereason that the improvement of the wettability is comparatively easy,and so forth. Collectors cast by the ABS resin are treated by immersingthem in strong acids or strong alkalis for several minutes to formhydrophilic groups on them in order to improve their wettability. Forexample, chromic mixed acid or sodium hydroxide are used as an acid oran alkali. However, the treatment has the following problems; adangerous working and the difficulty in the treatment of waste liquid.In addition, when the washing of the collector after the treatment isnot carried out completely, the following problems are considered to becaused; the waste liquid of the chemicals in the writing implementchanges the quality of ink and causes a definite default in the writingimplement. Although the danger in the job is high, the wettability ofthe ink collector to ink decreases with the elapse of time andtherefore, the treatment is not satisfied well.

[0019] On the other hand, a plasma treatment was carried out to improvethe hydrophilic property of ABS resin-made correctors (JP, 05-238186,A(1993)). Furthermore, a method to make a surface treatment with vinylmonomers after the plasma treatment was disclosed (JP, 05-238187,A(1993)). The plasma treatment is suitable for the surface treatment ofmaterials with smooth surface, but it causes a defect in the treatmentof correctors having concavo-convex surface because it cannot give agood result to treat the concave part of correctors.

[0020] This problem is similarly seen in the treatment of pen cores madeby fiber bundles and porous materials with an ink absorptivity. Namely,it is very difficult to treat the inner part of fiber bundles and porousmaterials by a plasma treatment.

[0021] In addition, as the surface treatment of ABS resins iscomparatively easy, an application of many general methods such as agrafting of hydrophilic monomers, an ionization radiation, a grafting byUV irradiation, and so forth is possible. However, as each of thesemethods has laborious processes and gives some problems in grafting suchas a surface irregularity and a difficulty to obtain a controlled amountof graft polymers, it's application is not suitable for the treatment ofmaterials such as correctors which need a precise structure.

[0022] When collectors and the other members in writing implements arecast with polyolefins such as polyethylene and poplypropylene, it isexpected to give a collector with an excellent chemical resistance, alightweight and a high-impact property and the other members of writingimplement. In addition, the application of these products does not causethe environmental pollution and the toxicity of components in combustiongas which are problematic in recent years. However, it is very difficultto improve polyolefin resins by the well-known technique for hydrophilicimprovement so far. Especially, as cast products of polyolefin resinsshould contain many kinds of additives such as stabilizers for polymerresins, chemical destaticizers, and so forth, their treatment to improvethe hydrophilic property is impossible as far as the products are usedas they are. Therefore, there is not an excellent method to give theimprovement expected in the hydrophilic property of collectors and theother members in writing implements as described above. If the techniqueto improve the hydrophilic property of polyolefins including chemicalstabilizers is established, its technique should be applicable for theother materials such as nylon, polyester, wool fiber, cellulose acetate,esters of polyacrylic acids, polyurethane, and so forth because thechemical treatment of these materials are easier than that ofpolyolefins. Therefore, the establishment of the technique for thesurface modification is expected.

[0023] (4) Prior Art for Battery Separators:

[0024] Battery Separators are used to provide a smooth electromotivereaction in batteries by holding the amount of the electrolyticsolution, while separating the positive electrode and negative electrodeof a chemical cell and preventing a short circuit from the former.Various requirements are dependent on the kind of batteries and a lot ofinventions were carried out.

[0025] For example, as the electrolytic solution of an alkaline cell isstrongly alkaline, a battery separator must be an alkali-proof material.A battery separator made of polyamide non-woven fabrics used from thepast has a fault that it elutes nitrogen oxides from the fiber andcontracting the life of a cell by repeat use. Therefore, batteryseparators made of fabrics of polyolefin fibers (a bicomponent fiber isalso included) such as polypropylene and polyethylene which wereexcellent chemical-resistant have been investigated. However, batteryseparators made of polyolefin materials with an excellent durable waterabsorption property are not seen at present.

[0026] When polyolefin fabrics with the improved water absorptionproperty are used as battery separators, they are immersed in an aqueoussulfuric acid solution of 40 w/w % concentration in lead storagebatteries, or in an aqueous solution of sodium hydroxide of 30 w/w %concentration in alkali batteries. As the charge-discharge process mustbe repeated in the batteries for use, the battery separators must givean excellent durability in the use for a long time as much as possible.For that purpose, a development of the method to produce hydrophilicpolymeric materials excellent in chemical resistance, oxidationresistance, and so forth is desired. Further, the method which makes itpossible to produce the hydrophilic polymeric material, easily, cheaplyand in large quantities is desired in industry.

[0027] Although various techniques mentioned in the above “(1) Prior Artfor Modification of Surface Property of Polymeric Materials” have beenapplied for the modification of materials for battery separators andsome methods have been proposed, the materials satisfying therequirements for battery separators are not obtained.

[0028] The present invention intends to overcome the defaults in theprevious methods described above and to provide a method for improvingthe surface property of polymeric materials which has an excellentdurability without lowering the practical strength. Furthermore, thepresent invention intends to provide materials with water-absorptionproperty modified for medical, sanitary, or cosmetic supplies such asdisposable diapers, sanitary protection supplies, bandages, gauze,plasters with disinfectants and materials for cleaning and face cleanserpack, and so forth, brackets for dentition orthodontics, water retentionmaterials useful for agriculture or greening in dry districts, materialsfor microorganism culture media, synthetic paper, filter media, medicalimplements (artificial organs, artificial joints, materials molded intubes, strings and plates, and so forth) and polymeric materials withimproved adhesive property and composites containing the said improvedpolymeric materials.

[0029] In addition, the aim of the present invention is applicable incommon for all kinds of synthetic resins, regenerated fibers and naturalfibers. Especially, the present invention gives a useful technique toimprove polyolefins whose chemical modification is known to bedifficult, and provides improved members of writing implements made ofpolyolefins which give the durability in the properties such as awettability to water-soluble ink, an ink-adsorptivity and an ink-holdingproperty.

[0030] Furthermore, the present invention intends to provide batteryseparators made of modified polymeric materials which give an excellentproperty in keeping electrolytic solutions in batteries, analkali-resistance, an acid-resistance, a lightweight and a highmechanical strength, and intends to prepare the battery separator withthe following properties cheaply and easily; that the hydrophilictreatment of the modified polymeric materials is made by real chemicalbonds and that the performance data of the battery are not changed inthe use for a long time, and to prepare the batteries containing thesebattery separators.

BRIEF DESCRIPTION OF DRAWINGS

[0031]FIG. 1 gives a drawing of a longitudinal section of a writingimplement of an example comprising an ink chamber filled with ink and anink collector with a comb-teeth shaped section in which a pen core isequipped.

[0032]FIG. 2 gives discharge curves of the batteries assembled withvarious separators which were continuously overcharged.

DISCLOSURE OF INVENTION

[0033] The present inventor investigated the method for improving thesurface property of polymeric materials wholeheartedly in order toattain the aims described above and discovered that a combination of animpregnation step, an activation step, a step of monomer grafting and astep of treatment with hydrophilic polymers is effective for theimprovement, and completed this invention.

[0034] Namely, the present invention relates to the method for modifyingthe surface of polymeric materials by the following sequential steps;

[0035] (1) subjecting the polymeric material to an impregnation step tocontact the polymeric material with a single or mixture of compoundshaving an impregnation property to the polymeric material in the mannerso that the content of the impregnated compound in the layer within thedepth of 100 microns from the surface of the polymeric material is inthe range of 0.1% to 40% by weight of the treated polymeric materialwithout any substantial deformation of the polymeric material; and

[0036] (2) subjecting the polymeric material produced in saidimpregnation step to an activation step to introduce carbonyl groupsinto the polymeric material; and

[0037] (3) conducting a step of monomer grafting to the polymericmaterial produced in said impregnation step and subsequent saidactivation step. This method is called “Modification method 1” below.

[0038] Or, the present invention relates to the method for modifying thesurface of polymeric materials by the following sequential steps;

[0039] (1) subjecting the polymeric material to an impregnation step tocontact the polymeric material with a single or mixture of compoundshaving an impregnation property to the polymeric material in the mannerso that the content of the impregnated compound in the layer within thedepth of 100 microns from the surface of the polymeric material is inthe range of 0.1% to 40% by weight of the treated polymeric materialwithout any substantial deformation of the polymeric material; and

[0040] (2) subjecting the polymeric material produced in saidimpregnation step to an activation step to introduce carbonyl groupsinto the polymeric material; and

[0041] (3) subjecting the polymeric material produced in saidimpregnation step and subsequent said activation step to a step oftreatment with hydrophilic polymers. This method is called “Modificationmethod 2” below.

[0042] Or, the present invention relates to the method for modifying thesurface of polymeric materials by the following sequential steps;

[0043] (1) subjecting the polymeric material to an impregnation step tocontact the polymeric material with a single or mixture of compoundshaving an impregnation property to the polymeric material in the mannerso that the content of the impregnated compound in the layer within thedepth of 100 microns from the surface of the polymeric material is inthe range of 0.1% to 40% by weight of the treated polymeric materialwithout any substantial deformation of the polymeric material; and

[0044] (2) subjecting the polymeric material produced in saidimpregnation step to an activation step to introduce carbonyl groupsinto the polymeric material; and

[0045] (3) subjecting the polymeric material produced in saidimpregnation step and subsequent said activation step to a step oftreatment with hydrophilic polymers; and

[0046] (4) conducting a step of monomer grafting to the polymericmaterial produced in said impregnation step and subsequent saidactivation step. This method is called “Modification method 3” below.

[0047] The present invention is explained in detail below.

[0048] (Polymeric Materials)

[0049] Polymeric materials used in the present invention include thepolymer material contained in each of a single polymer or a mixture ofpolymers, a modified single polymer or polymer mixture, a materialprepared by mixing or conjugating the polymers with glass, metal andcarbon fiber, and so forth. Both thermoplastic polymers andthermosetting polymers are used as synthetic polymers. Various methodsare exemplified for the preparation of these polymers, and all polymersprepared by these methods can be used in the present invention. Forexample, the following polymers are available; (1) homopolymers orcopolymers prepared by the addition polymerization of monomers selectedfrom olefins, vinyl compounds except olefins, vinylidene compounds andthe other compounds with carbon-carbon double bonds, (2) polymersprepared by the polycondensation such as polyesters and polyamides, andso forth or the mixture of these polymers or the modified polymers, (3)polymers prepared by the addition polycondensation such as phenol resin(containing Kynol (a commercial name of Japan Kynol Co., Ltd.), urearesin, melamine resin, xylene resin,and so forth or the mixture of thesepolymers or the modified polymers, (4) polymers prepared by thepolyaddition such as polyurethane, polyurea, and so forth or the mixtureof polymers or the modified polymers, (5) homopolymers or copolymersprepared by the ring-opening polymerization of cyclopropane, ethyleneoxide, propylene oxide, lactone and lactam, or the mixture ofhomopolymers or copolymers or the modified polymers, (6) cyclic polymersprepared by the polymerization of divinyl compounds (e.g.,1,4-pentadiene) or the mixture of homopolymers or copolymers or themodified polymers, (7) polymers prepared by the isomeric polymerization;e.g., alternative copolymer of ethylene and isobutene, and so forth, (8)homopolymers or copolymers prepared by the electrolytic polymerizationof pyrrole, aniline and acetylene, and so forth, or the mixture of thesehomopolymers or copolymers or the modified polymers, (9) polymersprepared by the polymerization of aldehydes and ketones,and so forth,(10) poly(ethersulfone) , (11) polypeptides, and so forth. As naturalpolymers, a single material or a mixture of cellulose, proteins andpolysaccharides or these derivatives, and so forth are given. In thepresent invention, the polymers made by the addition polymerizationdescribed above are preferably used. Monomers used in the additionpolymerization are not specially limited. Homopoymers or copolymers ofalpha-olefins such as ethylene, propylene, butene-1, hexene-1,4-methylpentene-1 and octene-1, and so forth and the mixture ofhomopolymers and/or copolymers are expedientially used.

[0050] In the present invention, “vinyl compounds except olefins” meanthe compounds containing vinyl groups. For example, the followingcompounds are given; vinyl chloride, styrene, acrylic acid, methacrylicacid, esters of acrylic or methacrylic acids, vinyl acetate, vinylethers, vinyl carbazole, acrylonitrile, and so forth. “Vinylidenecompounds except olefins” mean the compounds containing vinylidenegroups; vinylidene chloride, vinylidene fluoride, isobutylene, and soforth are exemplified. “Compounds containing carbon-carbon double bondsexcept olefins, vinyl compounds and vinylidene compounds give thefollowing compounds; maleic anhydride, pyromellitic dianhydride,2-butene acid, tetrafluoroethylene and chlorotrifuluoroethylene, and soforth and compounds containing two or more vinyl groups; butadiene,isoprene and chloroprene, and so forth are exemplified.

[0051] As preferable polymers prepared by the addition polymerization,homopolymers or copolymers prepared by the polymerization of two or moremonomers selected from these monomers and mixtures of these polymers canbe expedientially used. Especially, polyethylene, a copolymer ofethylene and the other alpha-olefins, polypropylene and a copolymer ofpropylene and the other alpha-olefins are preferably used. Thesecopolymers contain both of random copolymers and block copolymers.

[0052] As this invention is effective for improving a hydrophilicproperty of polyolefins whose chemical modification or treatment isconsidered to be extremely difficult, polyolefins are preferably used.

[0053] In addition to polyolefins, polymeric materials such ashomopolymers or copolymers obtained by the polymerization of one or moremonomers which are selected from the group comprising vinyl compounds,vinylidene compounds or compounds containing carbon-carbon double bonds;for example, poly(methacrylic acid ester)s resin, poly(acrylic acidester)s resin, polystyrene, polytetrafluoroethylene, copolymers ofacrylonitrile (acrylic fibers and their cast materials, ABS resin, andso forth), copolymers containing butadiene (synthetic rubbers), and soforth, polyamides (containing nylon and aliphatic or aromaticpolyamides), polyesters (containing polyethylene terephthalate andaliphatic or all-aromatic polyesters), polycarbonate, polyurethane,polybenzoate, polyethersulfone, polyacetal and various kinds ofsynthetic rubbers, and so forth are preferably used.

[0054] In addition to polymers described above, the following polymersare examplified; polyacetals, polyphenols, poly(phenylene ether)s,poly(alkyl-p-hydroxybenzoate), polyimides, poly(benzimidazole),poly-(p-phenylene benzbisthiazole), poly-(p-phenylene benzbisoxazole),poly(benzthiazole) and poly(benzoxazole), and the fibers of thefollowing materials are preferably used; cellulose acetate, regeneratedcellulose (viscose rayon, cuprammonium rayon, polynosic, and so forth),vinylon and a copolymer of vinylalcohol and vinylchloride (polychlal; acommercial name, Cordera), and so on. In addition, carbon fibers andnatural fibers; vegetable fibers such as cotton, hemp, flax, ramie andjute, and so on, and animal fibers such silk and wool, and so on arealso used. Moreover, the mixture or the conjugate materials containingthese polymers are preferably used.

[0055] The present invention is applicable for not only the polymericmaterials described above but also all kinds of polymers.

[0056] Even if the polymeric materials contain antioxidants,stabilizers, nucleation agents, flame retardants, fillers or bulkingagents, foaming agents, antistatic additives, and various additiveswhich are usually added in polymeric materials, they can be improved bythe present invention. In general, the modification of polymericmaterials containing the additives such as antioxidants and so on isknown to be very difficult because these additives prevent theactivation of the surface of the polymeric materials. In general, theexistence of additives such as antioxidants and so forth in polymericmaterials are considered to be not preferable for their modification,because these additives prevent the activation of the surface of thepolymeric materials. Therefore, it is considered to be preferable toprepare the polymeric materials with no additives or to remove additivesfrom the polymeric materials containing them. Contrary to this aspect,the technique in the present invention attains an effective surfacemodification for the polymeric materials containing additives such asstabilizers, and so forth. Therefore, this invention can be applicablefor a cast polymeric material itself which is prepared by a usualmethod.

[0057] (Form of Polymeric Materials)

[0058] In the present invention, the form of the moldings of thepolymeric materials to be improved is not especially limited. Forexample, fibers, woven fabrics, non-woven fabrics, cloth, a board, afilm, a sheet, a pipe, a rod, a hollow container, a box, a foam and alayered product, and so forth are available. From a viewpoint of theimprovement of the water absorptivity, especially moldings, such asfiber, textiles, a non-woven fabric, cloth, a film, and a sheet can beprocessed easily. Porous films and sheets prepared for filtrationmediums or synthetic papers are easily modified to give a durable waterabsorption property. In addition, when the present invention is appliedto the modification of the members or parts of products molded in apredetermined from, the polymeric materials which have not been usedconventionally were made usable. When the other various plasticmaterials (volts, nuts, chains, parts of electronics, caps, covers, andso forth) are treated by the present method, their wettability andadhesion property are improved and the electrification is decreased.

[0059] As fiber or textiles, various fibers, textiles and non-wovenfabrics of these fibers are preferably used. Each form of fibers isavailable; a fiber made of a single component, a mixture of two or moresorts of fibers, mixed fibers and a conjugate fiber (a sheath-core type,a side-by-side aligned type, a multicore type, a multi-island-in-the-seatype, a hollow-segment-pie type, and so forth).

[0060] (Members of Writing Implements)

[0061] Members of writing implements are composed of polymeric materialsand their forms are given as follows; an ink corrector, an ink tank, anink-guiding core, a pen core, a center rod in a pen, an ink-absorbingmaterials made of fibers, an ink-retaining sponge, a brush head of abrush pen, and a brush pen for painting colors, a brush pen for makeup,and so forth. Furthermore, a cap, an inner-cap and a plastic-mademouthpiece, and so forth are given. In addition, plastic members forsealing or fitting are given. Considering the structure of members, pencores, ink-introducing cores, ink-retaining members andtemporary-ink-retaining bodies which are made of porous materialsprepared by the fusion bonding or adhesive bonding with resin particles,or pen cores, ink-guiding cores, ink-retaining members andtemporary-ink-retaining bodies which are made by fusion bonding oradhesive bonding of polymer short fibers, polymer long fibers or amixture of short or long fibers of polymers.

[0062] (Battery Separators)

[0063] Preferable forms of polymeric materials for preparing batteryseparators are given as follows; non-woven fabrics, porous sheets,porous films, non-woven fabrics, board-like composites containingfibers, cloths, and so forth. In order to prepare separators for alkalibatteries, non-woven fabrics having a pore size of 1 to 200 microns, avacancy of 30 volume % to 80 volume %, a thickness of 20-500 microns, afiber diameter of 0.1-100 microns and a density of 5 g/m² to 100 g/m²are preferably used. Using these materials, battery separators whichgive a high wettability to electrolytic solutions, a high retainingproperty of electrolytic solutions, a good permeability for oxygengenerated from the positive electrode in the course of an electriccharge and an excellent strength can be produced. In addition, asseparators for lead-storage batteries, a composite which is prepared bybonding a coarse glass-fiber sheet with polyolefin fibers by the thermalfusion bonding or adhesive resins is preferably used. Battery separatorsfor the lead-storage battery as acid batteries require an appropriatethickness, a high strength and a high retaining property of electrolyticsolutions. Considering these conditions, non-woven fabrics having a poresize of 1 to 200 microns, a vacancy of 30 volume % to 80 volume %, athickness of 500 microns to 1200 microns, a fiber diameter of 0.1-100microns and a density of 100 g/m² to 300 g/m² are preferably used.

[0064] Each of modification method relating to the present invention isgiven below.

[0065] (Washing)

[0066] It is preferable to wash the surface of polymeric materials toremove some impurities with an appropriate liquid before the processing.For example, polyolefins, polyvinylchloride, polyvinylidene chloride,and so forth are washed preferably with toluene. Cellulose acetate,nylons, polyesters, polystyrene, acrylic resins, polyvinyl acetate,polycarbonate and polyurethane, and so forth are washed preferably withalcohols. Cellulose derivatives such as viscose rayon and cuprammoniumrayon, and so forth are washed preferably with an aqueous soap solutionfirst and with alcohols later.

[0067] (Impregnation Step)

[0068] The impregnation step is carried out by touching the polymericmaterials to the compounds which are impregnated in them at atemperature under the softening point of the polymeric materials; thesaid compounds having affinity to polymeric materials are used as theyare or as solutions or dispersants. In this step, polymeric materialsgive no essential deformations. The compounds used for this aim arecalled as “impregnants”. This impregnation step is explained as follows;the impregnants permeate in the crystal region of the polymericmaterials and make very small interstices in the materials. This stephas a role to proceed the subsequent activation step and grafting step.The impregnants contained in the polymeric materials can be removed bywashing after the subsequent steps.

[0069] The preferable range of the amount of impregnants in thepolymeric materials are given as follow; 0.1-40 weight % for thepolymeric materials whose thickness is below 1000 micron and the contentin the region of the materials within 1000 micron depth from the surfaceis 0.1-40 weight % for the polymeric materials with a thickness of over1000 micron. In the case of the polymeric materials with a thickness ofboards or a diameter of rods are below 20 mm, the impregnating contentis preferably 0.1-10 weight %.

[0070] (Impregnants)

[0071] As impregnants, each of compounds with an affinity to thepolymeric materials are used; inorganic or organic compounds andgaseous, liquid or solid compounds are similarly useful. Liquidimpregnants can be used as they are or their mixtures are used assolutions or dispersions prepared by mixing with the other liquids. Whenthe impregnants are solid, they are used as solutions, dispersions oremulsions by mixing with the other liquids. When the impregnants aregaseous, they are used as they are. The impregnants in the presentinvention contain a so-called solvent. However, the kind of impregnantsis not limited to this.

[0072] Impregnants are usually selected by considering the kind ofpolymeric materials which are processed. Compounds used in the carrierdyeing of synthetic fibers, especially polyesters or commercial carriersare preferably used. In addition, a lot of compounds corresponding tothe carriers can be used. These compounds can be widely useful for notonly polyesters but also polyolefins, polystyrene, polyacrylate resins,polyurethane, and so forth. Diphenyl, ortho- or para-hydroxybiphenyls,the other derivatives of diphenyl, sodium salicylate or its derivatives,halogenated aromatic compounds (for example, mono-, di- ortrichlorobenzene), and so forth are exemplified. These compounds can beused as solutions in organic solvents such as hexane, methanol, and soforth, dispersions in water or emulsions containing surfactants.

[0073] Moreover, liquids of organic compounds which have thecompatibility to the polymeric materials can be also used asimpregnants. As a matter of convenience, the following requirement isuseful to decide an impregnant for a polymeric material; a singlecompound or a mixture of plural compounds selected from the liquids oforganic compounds whose solubility parameters (SP) are close to those ofthe polymeric materials which are treated. It is preferable that apolymeric material is treated with a solvent whose difference of thesolubility parameter from that of the polymeric material is in the rangeof −2 to +2. When the difference of SP between a solvent and a polymericmaterial is smaller than this range, the polymeric material must betreated very quickly with the solvent at temperature much lower thanusual room temperature. The solvent does not dissolve the polymericmaterial but it should be only impregnated into the surface of it. Whenan organic solvent dissolves a polymeric material at high temperature,it can be used for a short time at low temperature where the polymer isnot dissolved by the solvent. As examples of liquid impregnants,toluene, xylene, decalin, tetralin, cyclohexane and a mixture ofdichloroethane and ethanol (1:2, volume ratio),and so forth are usefulfor polypropylene, a mixture of toluene and methanol (1:10, volumeratio), and so forth are useful for polystyrene and a mixture of phenoland hexane (1:10, volume ratio) , and so forth are useful forpolyethylene terephthalate.

[0074] Conditions for the impregnation step such as temperatures, times,and so forth are selected preferably by considering the form or shape ofthe polymeric materials to be treated. We can select the appropriateconditions for the aim of the treatment. For example, when a non-wovenfabric composed of polyolefin fibers with a diameter of 5-19 micron istreated, it is immersed in an impregnant (for example, toluene) for twominutes at room temperature and the impregnant in the fabric is removedby a centrifugal separator (a rotation rate: 500-2000 rpm). When thesurface of the polymeric material seems dry, the impregnation process isfinished. In the treatment of films, boards and cast materials (athickness about 2-5 mm) made of polyolefins, the material is immersed inan impregnant for 5-30 minutes at from room temperature to 70° C. andthe impregnant is removed similarly to the manner mentioned above. Theweight increase in the polymeric material through the impregnation stepis about 1-10 weight %.

[0075] In the impregnation step of wool fiber, it is immersed in amixture of an aqueous solution of sodium carbonate and methanol for 1-10minutes at room temperature, and the material is rinsed with methanoland the impregnant is removed by a centrifugal separator.

[0076] The present impregnation step is useful for the treatment ofmolded materials with a small surface area such as films and boards ormaterials which contain a lot of antioxidants and the other additives.

[0077] (Activation Treatment Step)

[0078] In the present invention, the activation treatment step means thetreatment to introduce carbonyl groups into the surface of materials. Inaddition to carbonyl groups, the activation treatment process gives theintroduction of functional groups or unsaturated bonds containing oxygenor nitrogen, and so forth to the materials. A preferable activationtreatment process is each of treatments such as a plasma treatment, anozone treatment, an ultraviolet light irradiation, a corona discharge, ahigh-voltage electric discharge, and so forth. Well-known facilities areavailable for the aim of the present invention. The extent of theactivation treatment is appropriately controlled by considering the aimof the treatment. An introduction of a trace amount of carbonyl groupsin polymeric materials is a preferable activation treatment for thepresent invention. Generally, activation treatments which were proposedso far are too hard to attain the aim of the present invention. As anindication of the activation treatment, an infrared spectroscopy (IR) oftreated polymeric materials is effective to observe the extent of theactivation treatment. For example, a ratio of the absorbance due tocarbonyl groups introduced in materials to that due to the crystallineregion which is not changed by the treatment is estimated by the baseline method and the result is used to see the extent of the oxidation bythe activation treatment.

[0079] For example, in the case of polypropylene, it is preferable thatthe ratio of the absorbance at around 1710 cm⁻¹ due to the carbonylgroups introduced in the polymer to the absorbance at around 973 cm³¹ ¹due to the methyl groups unchanged in the crystalline region is about0.2 or less.

[0080] A preferable method to determine the conditions of the activationtreatment is as follows: the relationship between a treatment time andan absorption due to introduced carbonyl groups in the activation ofobjective materials is previously observed and their relationalexpression is estimated. The condition of the activation treatment whichdoes not give a decrease in strength of the treated material isdetermined from the relational expression. When a decrease in thestrength is observed for the treated material even if the infraredspectroscopy indicates only the existence of a trace amount of carbonylgroups which is in a limit of the IR measurement, the appropriatetreatment time can be estimated by the extrapolation from the relationalexpression in the region which cannot be observed by IR. In this way, aneffective activation treatment for materials which gives no decrease inthe strength can be attained.

[0081] (Ozone Treatment)

[0082] The ozone treatment is carried out in order to cause a chemicalreaction, mainly oxidation of the surface of polymeric materials bycontacting ozone molecules to the polymeric materials. The ozonetreatment is performed by exposing polymeric materials to ozone. Anymethods of the exposing procedures can be available; for instance, toput a polymeric material under an ozone atmosphere for a given time, toexpose a polymeric material in a stream of ozone, and so forth. Ozonecan be generated by supplying air, oxygen, or gas containing oxygen suchas oxygen-added air, and so forth to an ozone generator. The ozonetreatment is carried out by introducing the obtained gas containingozone into a reaction vessel or a container in which polymeric materialsare involved. The conditions of ozone treatment such as a concentrationof ozone in a gas containing ozone, an exposure time, temperature, andso forth are appropriately determined by considering a kind and a formof a polymeric material and the aim of the surface modification.

[0083] Generally, a stream of oxygen or air with a flow rate of 20ml/min.−10 L/min. is used to generate ozone with a concentration from 10g/m³. to 200 g/m³., and polymeric materials are treated in it attemperature from 10° C. to 80° C. and a reaction time from 1 minute to10 hours.

[0084] For example, the treatment with an ozone concentration from 10 to40 g/m³ and a time from about 10 to 30 minutes at room temperature isavailable for the treatment of polypropylene fibers or polyvinylchloride fibers. When the specimen is a film, an appropriate ozonetreatment is carried out with an ozone concentration from 10 to 80 g/m³for the time from about 20 minutes to 3 hours at room temperature. Whenair is used instead of oxygen, the ozone concentration becomes about ahalf of that with oxygen.

[0085] It is considered that hydroperoxide groups (—O—OH), and so forthare introduced to the surface of polymeric materials by the reaction,mainly oxidation, using the ozone treatment and some of them areconsidered to be changed to hydroxide groups or carbonyl groups.

[0086] (Plasma Treatment)

[0087] A plasma treatment is carried out to introduce functional groupscontaining oxygen, nitrogen, and so forth to the surface of materials; apolymeric material is put in a vessel containing a gas such as argon,neon, helium, nitrogen, carbon dioxide, oxygen and air, and so forth andthe material is exposed to the plasma generated by a glow discharge. Itis considered that radicals are generated on the surface of thepolymeric material by the attack of the plasma. Subsequently, theradicals are exposed to air and reacted with oxygen to form carboxylicgroups, carbonyl groups, amino groups, and so forth are considered to beproduced on the surface of the polymeric material. Furthermore, theplasma treatment under a low pressure of nitrogen, oxygen or air canproduce functional groups directly on the polymeric material. Methods ofthe electric discharge for the generation of plasma are classified in(1) a direct current discharge, (2) a radio-wave discharge, (3) amicrowave discharge, and so forth.

[0088] (Ultraviolet Light Radiation Treatment)

[0089] An ultraviolet light radiation treatment is a method to irradiatean ultraviolet light (generally expressed by UV, or UV light in short)to the surface of polymeric materials. Low-pressure mercury lamps,high-pressure mercury lamps, super high-pressure mercury lamps, xenonlamps, metal halide lamps, and so forth are employed as a UV lightsource. It is effective that a polymeric material is treated with asolvent which can absorb UV light before the UV irradiation. Althoughany wave length of UV light is available, that of around 360 nm or alittle less is preferable to avoid the degradation of the material. Whena UV light is irradiated to a polymeric material, a part of the light isabsorbed by several chemical structures such as double bonds, and soforth in the surface region of the polymeric material and the absorbedenergy should break some chemical bonds to form radicals. The resultingradicals are considered to form carboxylic groups or carbonyl groups viaperoxides by the reaction with oxygen in air.

[0090] (High Electric Voltage Treatment)

[0091] A high electric voltage treatment is as follows. A polymericmaterial is put on a belt conveyor roller equipped in a tunnel-shapedimplement and the material is put on the belt. A high voltage such asseveral hundred thousands volts is charged between many electrodesequipped in the inner wall of the implement and the electric dischargewas made in air. It is considered that the electric discharge activatesoxygen in air and the surface of the material and that the oxygenincluded in the material surface forms polar groups in it.

[0092] (Corona Discharge Treatment)

[0093] A corona discharge treatment is as follows. A polymeric materialsis laid on a metal roller which is grounded, and a high voltage such asseveral thousands volts is added between the metal roller and theknife-shaped electrodes which are aligned with intervals of several mmdistance against the metal roller. A corona discharge is generatedbetween the metal roller and the electrodes in air and a polymericmaterial is passed through the space between the metal roller and theelectrodes. This method is suitable for films or thin materials.

[0094] The methods except the ozone treatment are based on an energyirradiation. When a polymeric material has a part which makes a shadowfor the irradiation, a technique is necessary to treat the shadow partby the irradiation. Therefore, the ozone treatment is preferable for thetreatment of materials such as a non-woven fabric and a fiber-assembledmaterial which give shadow parts derived from the material's structure.Besides, the ozone treatment is economical and preferable because of theeconomical equipment.

[0095] (Monomer Grafting Treatment)

[0096] In the present invention, monomers used for grafting are notlimited as far as they are graft polymerizable compounds; compounds withat least one carbon-carbon double bond, for instance, vinyl compounds orsimilar compounds to them are preferable. Hydrophilic monomers are morepreferable among monomers. As hydrophilic monomers, at least a singlemonomer or a mixture of monomers selected from the following group arepreferably used; acrylic, acid, methacrylic acid, vinyl acetate,2-butene acid, ethylene sulfonic acid, hydroxyalkyl acrylate,hydroxyalkyl methacrylate, acryl amide, vinyl pyridine, vinylpyrrolidone, vinyl carbazole, maleic anhydride and pyromelliticdianhydride. In the present invention, the use of acrylic acid ormethacrylic acid is especially preferable because their polymer give ahigh chemical resistance and a high water absorption property.

[0097] In addition, as vinyl monomers whose hydrophilic properties areless than hydrophilic monomers, the following monomers are alsoavailable; esters of acrylic acid, esters of methacrylic acid, vinylacetate, styrene, and so forth. A use of only hydrophilic monomers ispreferable, but, sometimes, a use of a mixture of hydrophilic monomerswith low hydrophilic monomers is effective for increasing the amount ofgrafting, as a result, the hydrophilic monomer residues contained in thegrafts on the polymeric materials can indicate a hydrophilic property.

[0098] As the methods of monomer grafting, each of the following methodsis available; (1) a method to carry out the monomer grafting in thepresence of catalysts or initiators (the general term is given as“initiators” below), (2) a method to carry out the monomer grafting byheating in the presence or absence of catalysts or initiators, and (3) amethod to carry out the monomer grafting by UV irradiation in thepresence or absence of catalysts or initiators.

[0099] The following initiators are exemplified; the combination ofperoxides (benzoyl peroxide, t-butylhydroxy peroxide, di-t-butylhydroxyperoxide, and so forth.), cerium ammonium nitrate (IV), persulfates(potassium persulfate, ammonium persulfate, and so forth.),oxidation-reduction initiators (oxidants: persulfates, hydrogenperoxide, hydroperoxide, and so forth., and inorganic reductants: coppersalts, iron salts, sodium hydrogen sulfite, sodium thiosulfate, and soforth, and organic reductants: alcohols, amines, oxalic acid, and soforth., and then the combination of the oxidants: hydrogen peroxide andso forth, and inorganic reductunts: copper salts, iron falts, sodiumhydrogensulfite, sodium thiosulfite, and so forth, or organicreductants: dialkyl peroxides, diacyl perozides, and so forth, andreductants: tertiary amines, naphthenates, mercaptans, organometalliccompounds (triethyl aluminium, triethyl boron, and so forth), the otherusual well-known initiators for radical polymerization, and so forth.

[0100] When acrylic acid is used as a monomer, a water-soluble initiatorsuch as cerium ammonium nitrate (IV) or potassium persulfate, and soforth. are preferably used. A water-insoluble initiator such as benzoylperoxide or N, N′-azobisisobutylonitrile (AIBN) is dissolved in methanolor acetone and the obtained solution is used after being mixed withwater. In the grafting by a UV irradiation, a photo-sensitizer such asbenzophenone , hydrogen peroxide, and so forth can be used, in additionto the initiators mentioned above.

[0101] A monomer grafting is carried out by general grafting methods.Namely, the monomer grafting can be attained by the reaction in each ofliquid phase, gaseous phase and solid phase.

[0102] When a water-soluble initiator is used, an appropriate amount ofthe monomer necessary for the treatment is dissolved in water. If awater-insoluble initiator is used, it is dissolved in an organic solventsuch as alcohols, acetone, and so forth which are miscible in water, andthe solution of the initiator is mixed with an appropriate amount ofwater, taking care not to precipitate. A polymeric material treated byan activation step or a step with a hydrophilic polymer explained belowis put in a solution of an initiator, and its monomer grafting iscarried out by adding a monomer in the mixture. The atmosphere in thereaction vessel is substituted by nitrogen if necessary. When a thermalgrafting is carried out, the reaction mixture is heated for a given timeat a given temperature. Furthermore, when a monomer grafting is carriedout by a UV irradiation, a UV irradiation is made to the reactionmixture for a given time at a given temperature. UV lamps are notlimited by special ones. A high pressure mercury lamp (for example, alamp, H400P produced by Toshiba Co., Ltd.) can be used. UV light withwavelength of about 360 nm monochromated by a filter is applicable, butUV light with a whole wavelength range generated by a UV lamp can bealso used.

[0103] When a monomer for grafting is a volatile compound, the vaporizedmonomer can be used for the grafting. Namely, a polymeric material whichwas pretreated is put in a sealed reaction vessel and a volatile monomer(for example, methyl methacrylate, styrene, and so forth.) is injectedinto the vessel. The reaction vessel containing the reaction mixture isevacuated to a given reduced pressure and the monomer is gasified in it.The reaction vessel is then made by a UV irradiation and the monomergrafting is attained.

[0104] When a vinyl monomer containing amide groups is used as a monomerfor the grafting, the Hoffman rearrangement to the graft polymerobtained in the polymeric material is preferably used according to themethod as described in JP,H8-109228, A(2006) by the present applicant.

[0105] (Hydrophilic Polymer)

[0106] The polymeric materials modified by the method of the presentinvention are improved in the following properties; by the method of theopreIn the present invention, “hydrophilic polymers” representswater-soluble polymers or polymers which do not dissolve easily in waterbut have a hydrophilic property. Specific examples of polymers are asfollows; poly(vinyl alcohol), sodium carboxymethyl cellulose,ethylene-vinyl alcohol copolymer, poly(hydroxyethyl methacrylate),poly(alpha-hydroxy vinyl alcohol), poly(acrylic acid),poly(alpha-hydroxy acrylic acid), poly(vinyl pyrrolidone) andpoly(alkylene glycol)s such as poly(ethylene glycol) and poly(propyleneglycol), and so forth. In addition, these sulfonates can also beavailable. In addition, sodium arginate, starch, silk fibroin, silksericin, gelatin, various kinds of proteins, polysaccharides, and soforth are exemplified.

[0107] (Step of Hydrophilic Polymer Treatment)

[0108] When a step of hydrophilic polymer treatment is carried out to apolymeric material which have been treated by an activation step, it ispreferable to attain the step in the presence of catalysts orinitiators. The catalysts or initiators used in “the monomer grafting”described above are similarly used in the step of hydrophilic polymertreatment.

[0109] In the step of hydrophilic polymer treatment, it is preferable touse an aqueous solution of a hydrophilic polymer. A water-solublepolymer is used as an aqueous solution. If a hydrophilic polymer is notsoluble easily in water, it can be used as a solution in an appropriatesolvent. The use of water-soluble polymers is explained below.

[0110] When a treatment with a water-soluble polymer is carried out inthe absence of an initiator, a polymeric material treated by theactivation step is put in an aqueous solution of the water-solublepolymer.

[0111] When a treatment with a water-soluble polymer is carried out inthe presence of an initiator, at first, an aqueous solution of thewater-soluble polymer is prepared. Then, if the initiator iswater-soluble, a given amount of it is dissolved in the aqueous solutionof the water-soluble polymer. If the initiator is not dissolved inwater, it is dissolved in an organic solvent such as alcohols, acetone,and so forth which are miscible with water, and then, the solution isadded in the aqueous solution of the water-soluble polymer. Then, apolymeric material obtained by the activation treatment is put in thesolution of the water-soluble polymer and the initiator. The inneratmosphere of the reaction vessel is desirable to be substituted withnitrogen gas, but the nitrogen atmosphere is not always necessary forattaining the process simply.

[0112] The temperature is not limited for the treatment with awater-soluble polymer and an initiator; usually, the temperature from10° C. to 80° C. is available, but that from 60° C. to 90° C. ispreferable. The treatment for a long time (for example, about 12 hours)at a high temperature is also carried out in order to obtain a durablehydrophilic property to a polymeric material.

[0113] (Uses)

[0114] Polymeric materials modified by the method of the presentinvention give the extremely improvement in the properties as follows;water absorption property, water retention property, adhesion property,chemical resistance, and so forth. These results can be available formany applications. As an adhesion property of a polymeric material isimproved, for example, it can be bonded to paper, wood, metal, and soforth, using general adhesives such as starch, poly(vinyl acetate),epoxy resin, poly(cyanoacrylate), and so forth. The present invention isapplicable for various materials which need an adhesion property.Furthermore, As the present invention is used for the improvement ofpolyolefins such as polypropylene and polyethylene whose improvement isknown to be difficult, it can be applied to modify the other many kindsof polymeric materials. To non-woven fabrics of polyolefin or that of amixture of polyolefin and another polymer, a water absorption of 7 to 10times as much as the original weight is given by this method. Inaddition, the improved materials give a good adhesion property andresistances to alkalis, acids and oxidants. Each of typical applicationsis described below, but the use of the present invention is not limitedto these applications.

[0115] (1) Tools or Materials for Wiping or Cleaning: at present, as adisposable wiping or cleaning material for a family use is made by thefollowing procedure and is marketed; as a main basic material, a mixtureof polyester fiber, polyolefin fiber, and the other synthetic fiber isprepared, and further, a rayon fiber is mixed with them to give ahydrophilic property and then, a surfactant is impregnated to the mixedfibers. If this disposable cleaning material is produced using thematerials prepared by the method of the present invention, the productgives a lightweight, a high strength, a high absorption property ofwater or an aqueous surfactant solution, and a high durability for use.It can be used repeatedly several times by rinsing with water.

[0116] (2) Water Absorptive Materials: materials with a water absorptionproperty prepared by the present invention are represented.

[0117] (3) Water Retention Materials: a hydrophilic polyolefin non-wovenfabric prepared by the present invention is useful for a water retentionmaterial which is available for supplying water to plants. To prepare awater retention material, the material of clothes, non-woven fabrics,fibers, and short-cut fibrous waste products are available. Fibers witha diameter of from 10 microns to 500 microns are preferably available.

[0118] (4) Medical, Sanitary or Cosmetic Supplies: disposable materialsuseful for medical, sanitary, or cosmetic articles are represented.Diapers, sanitary protections, bandages, gauze, sanitary napkins,disinfecting patches or tapes, the other medical implements, cosmeticsupplies or materials for cleaning, cleansing, face packing, makeup,padding, and so forth are exemplified.

[0119] The inner part of disposable diapers or sanitary protectionscontains materials having a water retention property which are made ofpulp, starch, polyacrylic acid, and so forth and the outside part ofthem is covered with a material having a water repellency which preventsthe passing of urine, water, blood, and so forth. Water which isgenerated from a body is passed through the inner hydrophilic non-wovenfabric and the water is absorbed in the materials with a water retentionproperty. A hydrophillc polypropylene is the most preferable material,because it is strong to water and not broken easily. However, thehydrophilic non-woven fabric used in an inner material is prepared onlyby dipping a non-woven fabric in an aqueous solution of a surfactant ora water-soluble reagent. The product prepared in this way should have nodurability to washing; the additive is easily removed by rinsing withwater. In addition, the effect of a surfactant to skins may be a problemto be worried. Thus, a development to prepare a polymeric material witha hydrophilic property, cheaply and easily is desired. Polyolefinmaterials improved in a water absorption or retention property which areprepared by the present invention are the most favorable materials forthe inner sewing cloth of the disposable diapers and sanitaryprotections. In addition, polymer materials with a high water absorptionproperty which are prepared by the present invention are also availablefor the water absorption material used in an inner pad of disposablediapers or sanitary protections. The hydrophilic material obtained bythe present invention gives a lightweight, a mechanical strength, asafety, and a durability for repeating uses. In addition, as thepolymeric material having a hydrophilic property or a water absorptionproperty which is obtained by the present invention is lightweight andstrong, and it can be impregnated with detergents, chemicals, adhesivesand so forth, it is available for gauze, a fiber product for wiping,disinfecting cloth patches or tapes, and the other cosmetic articles orsupplies. When they are used for disposable medical, sanitary, orcosmetic articles or supplies, a preferable material form is a cloth ora non-woven fabric, and its unit weight and thickness of the materialare appropriately selected. However, a fiber in cloth or a non-wovenfabric with a diameter of a range of 1 micron to 500 microns are usedeasily.

[0120] (5) Internal Materials for Clothes, Beds, and Bedclothes: thepolymer materials having a hydrophilic property or a water absorptionproperty obtained by the present invention are lightweight andmechanically strong. When their water absorption ability is controlledin a preferable extent, they are suitable for fiber products of clothesand an inner material for beds and bedclothes.

[0121] (6) Filter Mediums: filters of porous films made of hydrophobicmaterials such as polyolefins, polysulfone, a polyester, and so forth,have a mechanical strength and a low hydrophobic property as comparedwith paper filters. They are not available for the filtration of aqueoussolutions because of the low hydrophilicity. At present, they are coatedwith surfactants or water-soluble polymers in order to improve thehydrophilicity. However, the hydrophilic portions of these filters isnon-durable and is easily dissolved in water in the course of thefiltration. When the hydrophilic treatment of the present invention isapplied for the filter mediums, the filter mediums with a durable waterabsorption property can be obtained.

[0122] (7) Materials for Microbial Culture Mediums: as water retentionmaterials obtained by the present invention give a high water absorptionproperty, a high mechanical strength and a high microbial fertility,they are suitable for the materials for a microbial culture medium.Various forms of materials such as clothes, non-woven fabrics, fibersand cut disposable fibers are available. A diameter of component fibersin these materials is preferably from 10 microns to 500 microns.

[0123] (8) Dental Treatment Appliance: the treatment method of thepresent invention can modify the adhesion property of polymer materialswhich constitute materials for dental treatment. As the presenttreatment method can be available for various materials which need agood adhesion property, composite materials and fibers used infiber-reinforced plastics, it is also useful for the improvement of theadhesion property of a plastic appliance for dentition orthodontics (forexample, brackets) and the other appliances for dentition orthodontics.

[0124] (9) Members of Writing Implements: as the treatment method of thepresent invention can be applicable for usual resins such as polyolefinresins, nylon, polyester, polyurethane, and so forth, it is applied toimprove the property of members in writing implements for stationeryproducts, cosmetic implements, tools, and so forth. The followingwriting implements which need a wettability to ink, an ink-absorbingproperty and an ink-retaining property are exemplified; an inkcollector, an ink tank, an ink-guiding core, a pen core, a center rod inpens, an ink-absorbing materials made of fibers, an ink-storage sponge,a head of brush pen, a brush pen for painting colors, a brush pen formakeup tools, and so forth.

[0125] (10) Materials for Medical Supplies or Instruments: artificialblood vessels, artificial organs, artificial joints, and tube-, thread-or plate-like polymeric materials, and so forth. are exemplified. Forexample, medical supplies which are used by touching to human bodies orhuman organisms (catheters, tubes or other items for draining), bodyfluid absorbing materials, contact lenses, lenses for goggles, bandagesof synthetic fibers, gauze and instillation accessories are given.

[0126] (11) Polymeric Materials Composites: the adhesion property offibers which are used in polymer composites or fiber-reinforced plasticsis improved by the present Invention. The obtained fiber is used toproduce polymeric materials composites with a high strength.

[0127] (12) Synthetic Papers: synthetic papers made of polymicmaterials, such as polyolefins (polyethylene, polypropylene, and soforth.), polyesters and so forth,. are whitened by adding air bubbles orfillers, and they are used as the substitute of papers. The modificationof the hydrophilic property of the surface by the present invention canimprove an adhesion property and a printing property of syntheticpapers.

[0128] (13) Materials with Improved Adhesion Property: in addition tothe modification of the adhesion property of materials for various usesas described above, the present method can modify the adhesion propertyof various kinds of polymer films or mold products, and an adhesiveproperty with a homotypic or a different material can be improved.

[0129] (14) Application of Hydrophilic Film: the present invention givesa high hydrophilic property to polymer films of polyolefins, polyester,and so forth. For example, as a water-absorption polyester film obtainedby this invention gives a good adhesion property and a wettability towater, the antifog effect is acquired by sticking on glass or a mirror.

[0130] (15) Use for Battery Separator: battery Separators produced bythe method of the present invention give not only a high physicalstrength but also high chemical resistances to alkalis and acids. Theygive also a high absorption rate of various kinds of electrolyticsolutions and a high retention ability of them. Therefore, they can beuseful for each of primary batteries and secondary batteries. They canbe used in batteries with any shapes such as tubes, buttons and flatforms, and used in both of open cells and closed cells when they aresecondary batteries.

[0131] As primary batteries, an alkali-manganese battery using analkaline electrolytic solution, a mercury cell, a silver oxide cell, anair cell, a silver chloride cell, a lithium battery and a manganesebattery using an acid electrolytic solution, and so forth areexemplified. As secondary batteries, an alkaline storage battery usingan alkaline electrolytic solution (an Edison battery), a nickel-cadmiumbattery (a Jungner battery), a nickel-hydrogen battery, a lead storagebattery using an acid electrolytic solution, and so forth areexemplified. Battery separators prepared by the present invention can beused instead of paper-made battery separators which have been so farused in batteries.

Best Methods for Carrying Out the Invention EXAMPLE

[0132] Although this invention is explained by indicating examplesbelow, this invention is not limited to these examples and interpreted.In order to explain the excellent effect of the present invention, theexamples are compared with comparative examples.

[0133] Materials, reagents and tests or evaluation methods used inexamples and comparative examples are given below.

[0134] (A) Materials containing polymeric materials

[0135] (1) Polymeric materials used in examples and comparative examplesare listed in Table 1. Any manners to remove antioxidants, stabilizersand the other additives in the materials were not carried out.Abbreviations for words used here are given as follows. PP:polypropylene, PE: polyethylene, PET: polyethylene terephthalate, PSU:polysulfone, PP/PE or P/E: a mixture of polypropylene and polyethylene,and HPDE: high-density polyethylene.

[0136] (2) Materials for dental treatment : orthodontic brackets (size2.23×3.0×3.8 mm), which are made of polypropylene (each weight: about 31mg) or a nylon 12 (with a weight of about 32 mg) are reinforced withaluminum metal fittings.

[0137] (3) As members of writing implements or writing and paintingtools for makeup, the following various kinds of materials are used.

[0138] 1) A PP collector with a cross section of a comb-like shape: apolypropylene-made ink collector with a cross section of a comb-likeshape. This has a structure which is composed of two tubes; one tubewith comb-teeth gives an outside diameter 6mm and an inside diameter 2mm. The other tube is a cylinder with an outside diameter 6mm and anvoid diameter 4 mm. It's weight is 0.61 g and the length is 28 mm. Thiscollector is called as “PP collector 1” in short. Its shape is shown byFIG. 1.

[0139] 2) PP collector made by a laminate of sheet bodies : apolypropylene-made disc whose center is cored and has an embossedsurface (a number of embosses on a disk is 40) is prepared. A laminateof several number of the sheet bodies is used as an ink collector. Thedistance between each of sheet bodies is given by the height of theembosses on the disk. The disk gives a weight of 0.055 g. This collectoris called as “PP collector 2” in short.

[0140] 3) ABS collector with a cross section of a comb-like shape: anink collector made of ABS resin (a copolymer of acrylonitrile, butadieneand styrene) whose crosss section is a comb-like shape. and its weightis 0.61 g and the length is 28 mm. This collector is called as “ABScollector 1” in short.

[0141] 4) ABS collector made by a laminate of sheet bodies: an ABSresin-made disc whose center is cored and has an embossed surface (anumber of embosses on a disk is 40) is prepared. A laminate of severalnumber of the sheet bodies is used as an ink collector. The distancebetween each of sheet bodies is given by the height of the embosses onthe disk. The disk gives an outside diameter of 19.8 mm, an insidediameter of 5.0 mm and a weight of 0.061 g. This collector is called as“ABS collector 2” in short.

[0142] 5) An ink tank: a polypropylene resin-made tube with an outsidediameter from 7 mm (a point side) to 10 mm (an outlet) and an insidediameter from 2 mm ( a point side) to 8 mm (an outlet) and its lengthabout 8 mm.

[0143] 6) A pen core 1: This is made of PET resin. It's length is 37.0mm, the outside diameter, 1.8 mm and the weight, 0.188 g. It is made byfusing a bundle of PET fibers.

[0144] 7) A pen core 2: A slim pen core; whose commercial name is“Procky slim core”. It is made of PET resin. It's length is 27.0 mm, theoutside diameter, 2 mm and the weight, 0.0638 g. It is produced by afusion bonding of a bundle of PET fibers.

[0145] 8) An ink-guiding core: This is made of PET resin. It's length is22.5 mm, the outside diameter, 1.8 mm and the weight, 0.050 g. It ismade by a fusion bonding of a bundle of PET fibers.

[0146] 9) A brush head of a brush pen 1: this is made of polybutyleneterephthalate (PBT) resin. It's length is 150 mm, an outside diameter ofa bonded portion, 2.0 mm and the weight, 0.302 g. The brush head is apart for writing of a brush pen and it is used for writing as retainingink or sumi-ink in it. Besides, the brush head is used for brush pen fora makeup. As the brush is made with fine filament fibers of a syntheticpolymer, each fiber surface cannot give a wettability but it can absorbwater, water-soluble ink, or cosmetic chemicals because of acapillarity.

[0147]10) A brush head of a brush pen 2: this is made of nylon 66 resin.Its length is 250 mm, an outside diameter of a bonded portion, 5 mm andthe weight, 0.198 g.

[0148] 11) Stuffing fiber: it has a structure that PET fibers (adiameter, 2 denier) are stuffed in a tube made of PP film. Its length is78.0 mm and an outside diameter, 7 mm.

[0149] 12) An ink-storing sponge: polyurethane-made sponge. The weightis 16.0 mg and the thickness 2.0 mm. The form is a trapezoid (an upperside 120 mm, an under side 170 mm and a height 19 mm) which is cut in aspecial form.

[0150] (B) Reagents

[0151] (1) Polyvinylalcohol (PVA): its number-average degree ofpolymeriztion is 1500-1800.

[0152] (2) Sodium carboxymethyl cellulose (CMC)

[0153] (3) Acrylic acid

[0154] (4) Methacrylic acid

[0155] (5) Methyl methacrylate

[0156] (6) Sodium persulfate (SPS)

[0157] (7) Potassium persulfate (KPS)

[0158] (8) N, N′-Azobisisobutylonitrile (AIBN)

[0159] (9) Cerium ammonium nitrate (IV) (CAN)

[0160] (10) Benzophenone

[0161] (11) Methanol

[0162] (12) Sodium hydroxide

[0163] (13) Hydrochloric acid

[0164] (14) Toluene (Impregnant A)

[0165] (15) Sodium dodecylbenzene sulfonate (DBS): this was used as asurfactant.

[0166] (16) Decahydro naphthalene (a mixture of cis- and trans-isomers)(Impregnant B)

[0167] (17) ortho-Hydroxy biphenyl (OHB): o-Hydrobiphenyl (1 g) andsodium hydroxide (0.2 g), a surfactant (sodium dodecylbenzene sulfonate)were dissolved in water of 200 ml. This solution is called as ImpregnantC. Besides, a solution of o-hydroxy biphenyl (0.5 g) in methanol (300ml) was dispersed in water and used as a carrier (the dispersion isImpregnant D).

[0168] (18) Sodium salicylate (SS): sodium salicylate (1 g) wasdissolved in water (100 ml) and 0.5 ml of an aqueous hydrochloric acidsolution (concentration, 10% ) was added in it. The obtained solutionwas dispersed in water (the dispersin is Impregnant E).

[0169] (19) Diphenyl (DP): Diphenyl (2.5 g) and a surfactant (sodiumdodecylbenzene sulfonate, 0.2 g) were mixed in water of 200 ml (thesolution is Impregnant F).

[0170] (20) Carriant (a commercial product made by Toho chemical co.Ltd.): A carrier for the dyeing of polyesters or the other syntheticfibers. It contains anionic surfactants of aromatic ethers or similarcompounds. It was used as a dispersion in water (Carrier 1).

[0171] (21) Carrier TW200 (a commercial product made by Nikka chemicalco. Ltd.): a carrier for the dyeing of mixed fabrics containingpolyesters and wool. It contains methylnaphthalene and the othercompounds. It was used as a dispersion in water (Carrier 2).

[0172] (22) An acid dye, Orange G (Color Index name: C. I. Acid Orange10).

[0173] (C) Ozone Treatment: a specimen was put in a hard glass vessel of2L or 10 L volume (with an inlet and an outlet for gas), which wasequipped with an ozone generator (a product of Mitsubishi Denki Co.,Ltd., OS-IN). Then, ozone was generated by the ozone generator with anozone yield of 1 g/hour or an oxygen gas containing an ozone with aconcentration of 20 g/m³, were introduced into the reaction vessel witha flow rate of 800 ml/min for 1-120 minutes. Then, an ozone-free oxygenwas introduced into the reaction vessel for 10 minutes. Theconcentration of ozone was checked by an iodine titration. The extent ofoxidation of a material was checked by an infrared spectroscopy using aspecimen which was scrapped from the surface of the treated material.The change in the absorbance around 1710 cm³¹ ¹ (due to the absorptionby carbonyl groups) or the ratio of it to the absorbance around at 973cm³¹ ¹ were used for the judgement. The amount of ozone was 1 g/hour inexample if no remarks was given.

[0174] (D) Plasma Treatment: a specimen (fabrics, films, and so forth.)was placed on a position between two electrodes in a reaction bath of aplasma generator (a Yamato PR 500). After the pressure of the reactionbath was decreased to 0.27 Pa, a mixture of argon and oxygen (a volumeratio, 1:1) was introduced in the reaction bath until the pressure wasincreased to 5.6 Pa. A power supply was from 40 W to 100 W, and a glowdischarge was carried out mainly for from 30 seconds to 3 minutes at anoscillation frequency of 13.56 MHz. After the discharge, theintroduction of a mixture of argon and nitrogen was stopped, thepressure was raised to a normal pressure and the treated specimen wastaken out. The effect of the treatment was judged from a lowering of acontact angle of water to films.

[0175] (E) UV irradiation: In order to carry out an active treatmentsterp, a high pressure mercury lamp (an H400P produced by Toshiba Co.,Ltd.) was irradiated directly to a material from a distance of 10 cm. Inorder to carry out a grafting, a reaction mixture was put in aPylex-glass-made reaction vessel, and a high pressure mercury lamp (anH400P produced by Toshiba Co., Ltd.) was irradiated to the reactionvessel from a distance of 20 cm. In order to obtain a uniformirradiation, the reaction tube rotated itself and is revolved around theUV lamp. The reaction mixture means a solution of an initiator and amonomer in a solvent, or a gas such as air or nitrogen containingmonomer vapor.

[0176] (F) Evaluation of water absorptivity: measurements of a waterabsorptivity and a rate of water-absorption as described below.

[0177] (1) Water absorptivity: a specimen (size 10 cm×10 cm) was put ina beaker containing water, and it was stirred mildly with a glass rodfor one minute. Then, the specimen was taken out of the beaker and hungdown for 3 minutes (until water drops were not found). The increase inweight of the specimen (an amount of absorbed water) was estimated bythe subtraction of the weight of the dried specimen from the weight ofthe water absorbed specimen. The percentage of a weight of absorbedwater to the dried weight of the specimen gives “water absorptivity”.

[0178] Water absorption (%)=(a weight of absorbed water/a weight ofdried specimen)×100.

[0179] (2) Water absorption rate: a specimen of 1.5 cm width was hungand the portion of 1.5 cm length from the edge was immersed in water.The distance of water risied for one minute was observed (unit,cm/min.).

[0180] (G) Measurement of contact angle of water: a contact anglemeasuring apparatus (the CA-X of Kyowa Kaimen Kagaku Co., Ltd.) wasemployed. A water drop of about 1 mm diameter was dropped on a surfaceof a specimen by an injector at 20° C., and the contact angle wasestimated by a calculation from the figure of the water drop enlarged bya video camera.

[0181] (H) Washing fastness test: a specimen was put in an aqueoussolution (0.4 wt. %) of a weak-alkaline, fatty acid soap (a commercialname, Powder Soap of Lion Co., Ltd.) with a liquor ratio of 1/250 and itwas washed in the boiling state for 5 minutes with stirring. Then, thespecimen was completely rinsed with water and dried. A water absorption(%), a water absorption rate and a tensile strength were measured andthe values were compared with those before this washing process.

[0182] (I) Evaluation of dyeing property : ten orthodontic brackets wereput in an aqueous solution of an acid dye, Orange G (100 ml), and anacetic acid was added in the mixture to give the pH=5.0. The dyeingmixture was boiled for 15 minutes, then the boiling was stopped and itwas allowed to stand for 2 hours. The orthodontic brackets were washedin a boiling water and dried.

[0183] (J) Tensile strength test: a specimen was cut in a rectangle (thesize, 15 mm x 70 mm), and it was equipped on a tensile strength tester(a SFV-55-0-20M of Imada Seisakusyo Co., Ltd.) in the way that each partof 1 cm width from both edges of the specimen is pinched by the crampsof a tensile tester (a SFV-55-0-20M of Imada Seisakusyo Co., Ltd.) andit was drawn at a rate of 100 mm/min. Each specimen was drawn along itslengthwise direction or its cross direction. Only the values along thelengthwise direction are given in each of specimens.

[0184] (K) Peel strength test of adhesion

[0185] (1) film: a test piece was cut in a rectangle with a size of 30mm (vertical direction)×5 mm (a width). An adhesive 0.1 g is put on thepart of 5 mm width from the edge of the test piece and the test piecewas attached to a plywood board (2 mm in thickness, size 20 mm×10 mm) ora tag paper (0.2 mm in thickness, size 20 mmx 10 mm). A weight of 500 gwas put on the test piece attached to the plywood board or the tag papercovered with polyethylene film for 12 hours. Both of a portion of 10 mmwhich was not attached to the plywood and that of the another end whichwas not pasted to the film were pinched by the cramps of the tensiletester (a AGS-H of Shimadzu Seisakusyo Co., Ltd.) and it was drawn bythe tester at a rate of 30 mm/minute. The energy required for thepeeling of the test piece was estimated from the tester. In order tostandardize adhesion conditions, the relative value was calculated bysetting the measured value for the untreated test piece as 1.0 by thesimilar measurement.

[0186] Used adhesives were a polycyanoacrylate type adhesive(Aron-alpha, a product of Toa Gosei Co., Ltd.) for an adhesion to theplywood board and a stick-type paper use adhesive for stationery (acommercial name: UHF stick produced by Mitsubishi Pencil Co. Ltd.) foran adhesion to the tag paper.

[0187] (2) Orthodontic brackets: about 0.1 g of an adhesive was put onthe surface of treated or untreated brackets. Then, the bracket wasattached to an upper surface of a ceramic plate (size 10 mm×20 mm). Ametallic loop wire was connected to the bracket by hanging. The ceramicplate was pinched by an under cramp of a tensile tester (a SV-55-0-20Mof Imada Seisakusyo Co., Ltd.) and the metallic loop wire was pinched byan upper cramp. The specimen mounted on the tensile tester was drawn ata rate of 110 mm/min and the stress which was necessary for the peelingthe adhesion between the bracket and the ceramic plate was observed. Inorder to standardize the measured tensile strength, the observed valuefor the untreated bracket in the similar measurement was defmed to be1.0 and the peel strength of adhesion was estimated as a relative value.An adhesive containing polymeric methacrylic resin, and so forth whichis used by mixing methyl methacrylate monomer, poly(methyl methacrylate)and catalysts (a commercial name, Super Bond (San Medical Co. Ltd.) or ahomemade polymer solution were used as adhesives.

[0188] (3) Ink-absorbing sponge: each part of 5 mm width from the edgeof an ink-retaining sponge are pinched by the cramps of a tensile tester(a AGS-H of Shimadzu Seisakusyo Co., Ltd.) and it was drawn at a rate of100 mm/min.

[0189] (L) Retention of electrolytic solutions: a weight of a dried testpiece (size 5 cm×5 cm) was defined as W1. A specimen was dipped into anaqueous potassium hydroxide solution (30 wt. %) for 5 minutes. Thespecimen was taken out of the solution and was hung on for 3 minutes.The weight of the specimen W2 was measured when liquid drops were notseen. The following equation gives the absorption (%) of an electrolyticsolution.

Electrolytic solution retention (%)=100×(W 2−W 1)/W1

[0190] (M) Alkali-resistance of battery separators: a weight of a driedspecimen (size 5 cm×5 cm) was given as W1. A specimen was dipped in anaqueous potassium hydroxide solution (30 wt. %) for two weeks at 70° C.The specimen was taken out of the solution and its weight (W2) wasmeasured after hanging for 3 minutes. Then the specimen was washed withwater sufficiently and dried in vacuum, and the weight (W3) wasmeasured. An electrolytic solution (%) and a weight increase (%) wereobtained by the following equations.

Electrolytic solution absorption (%)=100×(W 2−W 1)/W 1

Weight decrease (%)=100×(W 1−W 3)/W 1

[0191] (N) Acid-Resistance of Battery Separators: a weight of a driedspecimen (size 5 cm×5 cm) was given as W1. A specimen was dipped in anaqueous sulfuric acid solution (40 wt. %) for two weeks at 70° C. Aftertwo weeks, the specimen was taken out of the solution and was hung onfor 3 minutes. The weight of the specimen (W2) was observed. Then, thespecimen was washed in water and dried sufficiently, and its weight W3was measured. In addition, its water absorptivity and tensile strengthwere observed. The following equations were used to estimate anabsorption (%) of an acid electrolytic solution and a weight decrease(%).

Electrolytic solution absorption (%)=100×(W 2−W 1)/W 1

Weight decrease (%)=100×(W 1−W 3)/W 1

[0192] (O) Oxidant-resistance test of battery separators: non-wovenfabrics treated for battery separators were dipped in an aqueoussolution of hydrogen peroxide (concentration, 40 wt. %) for seven daysat 50° C., Then, the specimens were washed sufficiently in water anddried, and the weight change and tensile strength were measured.

[0193] The battery performance test was carried out by the followingmethods, (P)-(T).

[0194] (P) Lowing of capacity of batteries incorporated with batteryseparators in the course of the self discharge: a treated specimen wasincorporated in a sealed nickel-hydrogen battery of a coin-size (anominal capacity, 500 mAh). When the property of the battery seemed tobe stable, they were charged to 120% of the capacity by an electricsource of 0.1 C(Coulomb). After four cycles of charge-dischargeprocesses, the percentage of an average value of a residual capacity (C)to the original value for each of batteries was estimated after the testfor two weeks at 45° C.

[0195] (Q) Charge/discharge method for batteries incorporated withbattery separators: the charge was carried out by charging directcurrent of 100 V into a sealed-type lead storage battery (with sixcells) until the voltage of the battery became 12 V. The discharge wascarried out by connecting the electric terminals to both poles of thebattery, and added a resistance to make the electric current to be 1.20A or 34 A.

[0196] (R) Change in capacity of a battery incorporated with a batteryseparator by the discharge for 5 hours: the time when the terminalvoltage of all cells in the battery changed from 12 V to 10.5 V(1.7V/cell) from the beginning of the discharge (an initial current of1.20 A) was observed.

[0197] (S) Change in capacity of batteries after discharge at lowtemperature: The time (electric discharge persistence time) when theterminal voltage of all cells in the battery changed from 12 V to 6 V(1.0 V/cell) by the discharge from the beginning of the discharge (aninitial current of 35 A) was observed at −15° C.

[0198] (T) Voltage of a battery incorporated with a battery Separatorafter a discharge for five seconds: the terminal voltage per one cell inthe battery was observed at 5 seconds after beginning the effectivedischarge at low temperature.

Example 1

[0199] Hydrophilic Treatment of Polypropylene Non-woven Fabric byModification 1 A PP non-woven fabric 1 (weight 1.0 g, size 20 cm×20 cm)which was given as Sample 1 in Table 1 was immersed in 100 ml ofImpregnant A (tolune) for 10 minutes at 50° C. in order to carry out theimpregnation step. Then, the PP fabric was rinsed with methanol andcentrifuged for one minute at a rate of 800 rpm. The increase in weightof the PP fabric was about 4 wt. %. Then, the PP fabric was treated withozone for 30 minutes in order to carry out the activation process. An IRspectroscopy of the treated or untreated PP fabrics was carried out andthe ratio of the absorbance at around 1710 cm³¹ ¹ (which is due to theabsorption of carbonyl groups) for the treated PP fabric to that ofuntreated PP fabric was 0.02. Then, the treated PP fabric was put in avessel containing 200 ml of water, 1 g of PVA, 20 mg of cerium ammoniumnitrate (IV) and 0.6 ml of acrylic acid, and the UV irradiation was madeto the reaction vessel from the distance of 20cm for 120 minutes at 30°C. After the treatment, the treated PP fabric was washed with a boilingaqueous solution of detergent for 10 minutes and washed with water anddried. The water absorption of the obtained specimen was 310% accordingto the water absorption test. The rate of water-absorption was 2.0cm/min. As the treated PP fabric gave excellent properties in a waterabsorption, a retention of electrolytic solutions, a highalkali-resistance, a high acid-resistance and a high oxidant-resistance,the present modification method is very effective for the preparation ofbattery separators.

Example 2

[0200] The same procedure as described in Example 1 was followed, exceptthat Impregnant B was used as an impregnant, except that a plasmatreatment for 30 seconds was carried out as an activation process andexcept that methacrylic acid was used as a monomer.

Example 3

[0201] The same procedure as described in Example 1 was followed, exceptthat Impregnant F was used as an impregnant, and except that a UVirradiation for 60 minutes was carried out as an activation process.

Comparative Examples 1-5

[0202] Comparative Example 1 gave the result with untreated specimens ofthe PP non-woven fabrics 1 used in Example 1. Comparative Examples 2-5were carried out by the same procedure as Example 1, except that one ortwo processes in Example 1 were omitted.

Example 4

[0203] The same procedure as described in Example 1 was followed, exceptthat Impregnant C was used as an impregnant, and except that a plasmatreatment for 30 minutes was carried out as an activation process.

Comparative Example 6

[0204] It gives the result with untreated PP plain fabric.

Comparative Example 7

[0205] The same procedure as described in Example 4 was followed, exceptthat the impregnation treatment was omitted, and except that 10mg ofAIBN was used as an initiator of grafting instead of CAN.

Example 5

[0206] The same procedure as described in Example 1 was followed, exceptthat a PET non-woven fabric of Sample 4 (a size, 10 cm×10 cm) was used,except that an aqueous dispersion of Carrier 2 (5 g of the reagent wasmixed with 200 ml of water) was used for the impregnation process,except that an ozone treatment was carried out as the activation processand except that a thermal grafting was carried out at 80° C. using 10mgof AIBN as an initiator instead of CAN.

[0207] Example 6

Grafting in the Gas Phase

[0208] An impregnation process of a PET non-woven fabric of Sample 4 (asize, 10 cm×10 cm) was carried out in Impregnant A for 5 minutes at 30°C. As the activation process, an ozone treatment for 20 minutes wasattained. The monomer grafting was carried out as follows; the PETnon-woven fabric treated by the impregnant and activation processes wasput in a glass-made reaction vessel. The vessel was evacuated and 0.2 mlof MMA was put into it. After vaporizing the MMA in the vessel by anevacuation to some extent, a UV irradiation to the reaction vessel wascarried out for 90 minutes. The treated PET non-woven fabric gave amonomer grafting of 5%. It gave good improvements in the adhesionproperty and the dyeing property.

Comparative Examples 8-12

[0209] Comparative examples 9-12 were carried out by the same procedureas described in Example 1, except that one or two processes wereomitted.

Example 7

[0210] A PP/PET non-woven fabric of Sample 3 in Table 1 was used as aspecimen. Impregnant C was used for the impregnation step and a plasmatreatment for 30 minutes was carried out as an activation process. Athermal monomer grafting was carried out for two hours at 80° C. using amonomer, methyl methacrylate and an initiator, KPS.

Example 8

[0211] The same procedure as described in Example 7 was followed, exceptthat a PP/PET non-woven fabric was used as a specimen, and except thatImpregnant E was used for the impregnation step and except that aninitiator, KPS and a monomer, acrylic acid were used.

Comparative Example 13

[0212] It gives the result with an untreated PP/PET non-woven fabric.

Example 9

[0213] A PET film of Sample 12 was used. The PET film (weight 1.62 g,size 15 cm×15 cm) was immersed in 100 ml of an Impregnant E for 15minutes at 70° C. as an impregnation step. Then, the PET film was rinsedwith methanol and the waste of the impregnant was wiped off with a paperand dried for 5 minutes at room temperature. Then, the PET film wastreated by an ozone treatment as an activation process. Subsequently,the treated PET film was put in a Pyrex glass-made reaction vesselcontaining a solution of 1.2 ml of acrylic acid in 200 ml of water andan UV irradiation to the reaction vessel was carried out for 2 hours at30° C. After the process, the PET film was washed with an aqueoussolution of a detergent for one minute at 60.° C., washed for one minutewith a boiling water, washed with water and dried. The water absorptionof the obtained specimen was 90% and its contact angle of water was63.degree. Its peel strength of the adhesion to a label paper bound witha stick-type paper use adhesive for stationery was 4 when that for anuntreated PET film was 1.

Comparative Examples 14-18

[0214] They give the results with untreated PET films and the resultsobtained by the same procedure described in Example 9, except that oneor two processes were omitted.

Example 10

[0215] A HMPE plate of Sample 13 (a weight, 3.84 g and a size, 10 cm×10cm) was immersed in 100 ml of Impregnant B for 15 minutes at 70. ° C. asthe impregnation step. Then, the specimen was rinsed with methanol andthe waste of the impregnant was wiped off with a paper and dried for 5minutes at room temperature. Then, the specimen was made by an ozonetreatment for 30 minutes as the activation step. Subsequently, themonomer grafting by the UV irradiation similar to Example 1 was carriedout using 180 ml of water, 20 mg of CAN and 1.0 ml of acrylic acid.

Comparative Examples 19

[0216] It gives the result with an untreated HMPE plate of Sample 13.

Comparative Examples 20-23

[0217] They give the results obtained by the same procedure described inExample 10, except that one or two steps were omitted.

Example 11

[0218] A PP film of Sample 11 (a weight, 0.38 g and a size, 15 cm×15 cm)was immersed in Impregnant C (100 ml ) for 10 minutes at 70. ° C. as animpregnation process. Then, the specimen was rinsed with methanol andthe waste of the impregnant was wiped off with a paper and dried for 5minutes at room temperature. Then, the specimen was made by an plasmatreatment for 30 seconds at 30° C. as the activation step. Subsequently,the monomer grafting by the UV irradiation similar to Example 1 wascarried out using 180 ml of water, 20 mg of AIBN and 1.0 ml of acrylicacid.

Comparative Example 24

[0219] It gives the result with untreated PP films.

Comparative Examples 25-28

[0220] The same procedure described in Example 11 was followed, exceptthat one or two processes were omitted.

[0221] The above results are summarized in Table 2. In Table 2, thewater absorption 1 gives the water absorption % of the specimen afterthe processes which were washed with an aqueous detergent solution andwater at room temperature and dried, the water absorption 3 gives thewater absorption % of the specimen after the treatment steps which wereprocessed by the three times of washing with a boiling aqueous detergentsolution and water and a drying. In Table 2, ozone, plasma andultra-violet light are represented by OZ, PL and UV, respectively. Inthe results in Examples 9-11 and Comparative Examples 14-18, theadhesive used for the measurement of the peel strength of the adhesionis an adhesive containing mainly polycyanoacrylate for Example 10 and

Comparative Examples 19-23, and a stick-type paper use adhesive forstationery was used for the other Examples and Comparative Examples.Example 12

[0222] A Method to Give Hydrophilic Property to Carbon Fiber and its Usefor Composite

[0223] Carbon fiber (6.0 g) of Sample 9 in Table 1 was used as aspecimen. The specimen was immersed in methanol for 30 minutes at 50° C.as the impregnation process. Then, the treated specimen was centrifugedfor one minute at a rate of 800 rpm. Then, the specimen was put in ahard glass vessel with 1.5 mm thick. The ozone was regenerated asfollows; oxygen was introduced into an ozone-regenerator with a flowrate of 100 mil/min and ozone with a concentration of 40 mg/L wasregenerated. The ozone was introduced in the reaction vessel for 30minutes at 20° C., and subsequently, ozone-free oxygen was introduced inthe vessel for 10 min. Then as the monomer grafting step, the treatedspecimen was put in a glass-made reaction vessel and acrylic acid 1.2ml, water 200 ml and methanol 5 ml were added in it. The same UVirradiation to the reaction vessel as described in Example 1 was carriedout for three hours as the grafting step. Then, the reaction mixture wasput in a large amount of water. The carbon fiber attached by polymerswas taken out of the water. The treated carbon fiber was washed in aboiling aqueous detergent solution, three times. The grafting was 15%.After drying, the carbon fiber gave the water absorption 200% (that ofuntreated carbon fiber, 60%).

Comparative Example 29

[0224] The same procedure as described in Example 12 was followed,except that the impregnation process was omitted. The grafting % of thetreated specimen was 4.2% and its water absorption was 130%.

Comparative Example 30

[0225] The same procedure as described in Example 12 was followed,except that the activation process was omitted. The grafting % of thetreated specimen was 3.0% and its water absorption was 110%

Comparative Example 31

[0226] The same procedure as described in Example 12 was followed,except only the UV irradiation grafting was carried out and the othersteps were omitted. The grafting % of the treated specimen was 1.0% andits water absorption was 100%.

Example 13

[0227] The carbon fiber processed in Example 12 was mixed with an epoxyresin adhesive and a rod of 5 mm width×5 mm thickness×100 mm length wasprepared by drying the mixture. As a reference, a rod with similar sizeto the above one was made with the epoxy resin adhesive and untreatedcarbon fiber. The tensile strength of the epoxy resin rod reinforced bythe hydrophilic carbon fiber was 40 times larger than that of thereference rod containing untreated carbon fiber.

Example 14

[0228] Hydrophilic Treatment of Wool Fiber Fabric

[0229] Wool fiber (1.0 g) of Sample 10 in Table 1 was used as aspecimen. The specimen was immersed in a solution of anhydrous sodiumcarbonate (10 mg) in methanol (10 ml) and water (90 ml) for 30 minutesat 50° C. as the impregnation step. Then, the treated specimen wascentrifuged for one minute at a rate of 800 rpm. Then, the specimen wastreated by an ozone treatment similarly to Example 12. Then as thegrafting step, the treated specimen was put in a glass-made reactionvessel and acrylic acid 1.2 ml, water 200 ml and methanol 5 ml wereadded in it. The UV irradiation was carried out to the reaction vesselfor two hours similarly to Example 12 under an air atmosphere. The woolfiber fabric attached with polymers was take out of the reaction vessel.The treated specimen was washed in a boiling aqueous solution of adetergent three times. The grafting was 18%. The obtained treated woolfiber fabric gave a water absorption 300%.

Comparative Example 37

[0230] The same procedure as described in Example 14 was followed,except that the impregnation process was omitted. The graftingpercentage of the treated specimen was 4.2%.

Comparative Example 38

[0231] The same procedure as described in Example 14 was followed bycarrying out only the monomer grafting step by the UV irradiation,except that the other processes were omitted. The grafting percentage ofthe treated specimen was 1.5%.

Comparative Example 39

[0232] The same procedure as described in Example 14 was followed,except that the activation process was omitted. The grafting percentageof the treated specimen was 1.6%.

Example 15

[0233] Water Absorption Test

[0234] Treated or untreated wool fiber fabrics were floated on thesurface of water, keeping the thin direction of the specimen parallel tothe surface. The time for the specimen absorbed water to sink wasobserved. The short time indicates a high hydrophilic property. The timeobserved for an untreated wool fiber fabric was 60 minutes. The timeobserved for the wool fiber fabric treated in Example 14 was one secondand those observed for the wool fiber fabrics obtained by

Comparative Examples 37, 38 and 39 were 15 seconds, 28 seconds and 30seconds, respectively. Example 16

[0235] Improvement of the Hydrophilic Property of Polypropylene-MadeSynthetic Papres

[0236] The same procedure as described in Example 2 was followed totreat porous PP films of Sample 14 in Table 1 which were used assynthetic papers, and their hydrophilic property was improved. It waspossible to write characters with water-soluble ink on the treatedsynthetic papers. In addition, it was possible to bond label papers tothe treated synthetic papers with water soluble glues (starch, CMC, PVAglues, and so forth.). As the label paper bond to the treated syntheticpaper was broken in the tensile strength measurement, its peeling wasimpossible.

Example 17

[0237] Improvement of the Hydrophilic Property of Porous PolyethyleneFilm and its Application for Filters.

[0238] The same procedure as described in Example 9 was followed, exceptthat porous polyethylene film of Sample 15 in Table 1 was used as thespecimen. The water absorption of the treated PE film was 200% (that foran untreated specimen was 5%). The contact angle of water to the treatedspecimen could not be observed (it seemed to 0.degree. that of theuntreated specimen 120.degree.). Furthermore, the weight increase in thetreated specimen was 2%. The obtained hydrophilic porous polyethylenefilm gave the alkali-resistance and the acid-resistance, and it wasuseful for the filtration of components contained in water.

Example 18

[0239] Improvement of the Hydrophilic Property of Porous PolysulfoneFilm and its Application for Filters.

[0240] The porous polysulfone film of Sample 16 in Table 1 (weight 0.5g, size 10 cm×10 cm) was immersed in an aqueous methanol solution(methanol 10 volume %) for one minute at room temperature as theimpregnation step. Then, the specimen was treated with ozone for twominutes as the activation step. The other procedures were carried out inthe same manner as described in Example 17.

[0241] The water absorption 3 of the treated polysulfone film was 250%(that for a untreated specimen was 5%). The contact angle of water tothe treated film could not be observed because of the high waterabsorption property (that of the untreated specimen 120.degree.).Furthermore, the weight increase in the treated specimen was 2%. Theobtained hydrophilic porous polysulfone film gave the alkali-resistanceand the acid-resistance, and a high heat-resistance (it was thermallytreated three times in an autoclave at 120° C.). The obtained treatedporous polysulfone film useful for the filtration of componentscontained in water.

Example 19

[0242] Improvement of Hydrophilic Property of PP Non-woven Fabric 2 by“Modification Method 2”.

[0243] A PP non-woven fabric 2 (weight 1.0 g and size 15 cm×15 cm) whichis given as Sample2 in Table 1 was immersed in 100 ml of Impregnant Ffor 5 minutes at 50° C. Then, the fabric was centrifuged at a rate of1000 rpm. When the increase in weight of the PP fabric was 4 wt. %, itwas treated with ozone for 30 minutes at 20° C. in order to carry outthe activation process. Then, the treated specimen was put in a reactionvessel. Furthermore, after 20 ml of water, 60 mg of potassiumpersulfate, 0.3 g of polyvinyl alcohol and 6 ml of methanol were addedin the reaction vessel, the reaction mixture in the vessel was allowedto stand for two hours at 80° C. Then, the specimen was washed withwater and washed with an aqueous solution of a detergent. The waterabsorption 3 of the obtained treated PP non-woven fabric 2 was between800% and 1000%. The weight increase in the specimen after thehydrophilic treatment was not measured within the accuracy of 0.1 mg.The result is given in Table 2. After six times of washings with adetergent, the obtained specimen kept a water absorption of over 810%.The obtained treated specimen was completely applicable for the materialwhich could be used as materials with the water absorptivity.

Example 20

[0244] Improvement of Hydrophilic Property of PP Non-woven Fabric 2 by“Modification Method 2”.

[0245] The same procedure as Example 19 was followed, except that CMCwas used for the hydrophilic polymer treatment instead of PVA. The waterabsorption percentage of the treated specimen was 600-900% and the waterabsorption property gave a durability.

Example 21

[0246] Application as a Microbial Culture Medium

[0247] Each of improved non-woven fabrics obtained by the same procedureas Examples 19 and 20 was cut in two pieces of a size of 2 cm×2 cm, andthey were aligned in a petri dish of 8 cm diameter and 2 cm depthwithout an overlapping. A bouillon/agar solution 100 ml was prepared bydissolving meat extract (191 wt. %), polypeptone (1 wt. %), sodiumchloride (0.5 wt. %) and agar (0.5 wt. %) in water. The agar in themixture was dissolved by using a microwave oven, and a bouillon/agarsolution 50 ml was infiltrated through said non-woven fabrics preparedby the present method. Then, the mixture was cooled down to the roomtemperature. The non-woven fabrics containing the bouillon/agar solutionwere put in the test tubes, which had been autoclaved for 15 minutes at120° C. These test tubes were allowed to stand at 37° C. overnight. Thefollowing day, after confirming the asepsis,. microbes (Escherichia coliK-12 strain, Salmonella Typhirnurium LT-2 strain and Bacillus subtilisMarburg strain, and so forth.) were planted on the fabrics, and theywere cultivated overnight at 30-37° C. A microscopic observation showedthat each of the microbes was growing well.

Comparative Example 40

[0248] The same procedure as described in Example 19 was followed,except that the impregnation process was omitted. The water absorptionpercentage of 780% of the treated specimen decreased to 400% after threetimes of washings with an aqueous detergent solution.

Example 22

[0249] Improvement of Hydrophilic Property of Sample 6 by “ModificationMethod 3” and its Application for Cleansing/Wiping Cloth

[0250] A polypropylene/polyester sheath-core type conjugated fiber,PP/PE non-woven fabric (2.4 g) which is given as Sample 6 in Table 1 wasimmersed in 10 ml of Impregnant D for 10 minutes at 30° C. as theimpregnation step. Then, the fabric was centrifuged (a rotation rate,1000 rpm) until the extent that the surface looked dry apparently. Theweight increase in the specimen after the step was about 4%. Then, thespecimen was treated with ozone for 30 minutes. Then, the ozone-treatedspecimen was put in an Erlenmeyer flask, and 5 ml of methanol, 100 ml ofwater, PVA (0.5 g) and potassium persulfate (0.1 g) were added in theflask and the flask was allowed to stand for 2 hours at 80° C. Afterthis treatment, the specimen was washed sufficiently with water at 60°C. Then, after squeezing water, the treated no-woven fabric was put in avessel together with water (400 ml), CAN (10 mg) and acrylic acid (5ml). The reaction mixture was allowed to stand for 2 hours at 80° C.under air atmosphere. After the treatment, the treated fabric was washedwith an aqueous solution of a detergent at 60° C., three times (500 mlof water was used in each washing). After drying the treated specimen,it gave a water absorption of 2310%. That of an untreated non-wovenfabric was 350%. The weight increase in the specimen by the hydrophilictreatment was 4%. The present modification method gave higher waterabsorption (%) and faster water-absorption rate and more durable waterabsorption property than the procedure by “Modification 1” (Modificationmethod 1 gave about 1400% for the same specimen as used here), and thetreated specimen was useful for the cleansing/wiper application. Afterabsorbing water to the treated non-woven fabrics (water absorption,about 2000%), ten pieces of the treated non-woven fabrics weresuperposed. The superposed non-woven fabrics were mounted on a cleansingmop and the mop was used to clean a wooden floor. After using it, it wasrinsed with water and used repeatedly. It could be used over ten times.

Example 23

[0251] Hydrophilic Treatment of PP Non-woven Fabric 2 and an Applicationfor Disposable Sanitary Supplies.

[0252] A model of disposable diaper was prepared as follows: thehydrophilic polyolefin non-woven fabric obtained by the procedure ofExample 19 was used for an inside cloth, an untreated hydrophobicpolyolefin non-woven fabric was used for the outside cloth, and a waterretention agent (water-absorption polymers; pulp, starch or polyacrylicacid and its derivatives, and so forth.) was used as a core material.Namely, an untreated hydrophobic polypropylene non-woven fabric was puton the bottom, and a water retention polymer was put on it, and thehydrophilic polyolefin non-woven fabric 2 of the present invention wasput on the top. When water was poured on the diaper model, water waspenetrated quickly through the hydrophilic polyolefin non-woven fabric 2and absorbed by the water retention agent. Thus, the non-woven fabricimproved in the water absorption property prepared by the presentinvention was available preferably for the material for disposablediapers and sanitary materials or sanitary protections.

Example 24

[0253] Improvement of Adhesion Property of a Dentition OrthodonticAppliance

[0254] MMA was grafted to 20 pieces of polypropylene-made orthodonticbrackets (0.622 g) by the same procedure as described in Example 6.Polymerization inhibitors contained in MMA were removed before use. Thetreated brackets gave a good adhesion property in the adhesion toceramic materials for the dentition with a polymerizable acrylic resinadhesive, and the breakdown of the bracket bonded to the ceramics wasobserved in the peel strength test. In addition, the orthodonticbrackets made of nylon 12 and the other polymers gave the same resultsas those described above. After dipping the modified brackets which werebonded to the ceramic materials in water for one year at 30° C., theloweing in the adhesion force between them was not observed. Bothbrackets of PP and nylon 12 which were modified by the present inventionwere not dyed with an acid dye (Orange G) in the dyeing test.

Comparative Example 41

[0255] PP/PE non-woven fabrics modified by the hydrophilic treatmentwith well-known surfactants (the non-woven fabrics produced by JapanVilene co. Ltd. were impregnated with surfactants) were prepared and thesame tests as Example 1 were carried out. The results are given below.

[0256] 1) Alkali-resistance test: the water absorption property of thetreated fabric decreased to the original value of the untreated fabric,5%.

[0257] 2) Acid-resistance test: after washing sufficiently with water,the water absorption property of the treated fabric decreased to theoriginal value f of the untreated fabric, 5%.

[0258] 3) Oxidant-resistance test: after washing sufficiently with waterand drying, the water absorption property of the treated fabricdecreased to the original value of the untreated fabric, 5%.

Comparative Example 42

[0259] Grafting of Acrylic Acid to PP Non-woven Fabric 1 by a Well-knownUV Irradiation.

[0260] PP non-woven fabric1 (weight 1.2 g and size 7.7 cm×10 cm) was putin a reaction mixture containing acrylic acid monomer 20.0%, water78.8%, benzophenone 0.2% and methanol 1.0% (each % represents weight %),and the reaction mixture was made by the UV irradiation for two hours.After the reaction, the product was jelled with resulted polymers, butwhen the product was washed with a boiling aqueous solution of a soap, asodium salt of a fatty acid for 10 minutes and water, the specimen wasseparated from the polymers dissolved in the washing process. The waterabsorption percentage of the treated non-woven fabric was 100% (that ofthe untreated non-woven fabric was 48%). Its grafting percentage was 1%.Namely, the grafting by the UV irradiation to the present non-wovenfabric seemed to be difficult, and the polymer composed of only acrylicacids which was formed seemed to be dissolved and removed from thefabric by washing with a boiling aqueous detergent solution. The waterabsorption of the treated no-woven fabric was decreased by the treatmentwith acids or alkalis.

[0261] Examples for writing materials are described below.

Writing Implement Example 1

[0262] Hydrophilic Treatment of PP Collector 1 by Modification 1.

[0263] The 40 pieces of PP collector 1 were immersed in 200 ml ofImpregnant D for 5 minutes at 50° C. in order to carry out theimpregnation step. Then, the collectors were rinsed with methanol andcentrifuged for two minutes at a rate of 1000 rpm. The impregnantimpregnated in the collectors was about 2% in weight. Then, the PPfabric was treated with ozone for 30 minutes as the activation process.The IR spectroscopy of the surface of the treated collectors was carriedout and the ratio of the absorbance at around 1710 cm³¹ ¹ (which is dueto the absorption by carbonyl groups) to that at around 973 cm³¹ ¹ was0.02. Then, the treated collectors were put in a Pyrex-glass vesselcontaining 200 ml of water, 10 ml of acrylic acid and 100 mg ofpotassium persulfate. After putting a cover on the vessel, The UVirradiation was made to the reaction vessel for two hours. The treatedcollectors were taken out of the reaction mixture and was washed in aaqueous solution of a detergent for 10 minutes at 60° C. and washed withwater and dried. The collectors improved in the hydrophilic propertywere obtained. The obtained improved collectors were reversed. Theportion of a distance of 3 mm from the end of the collector was immersedin water or an aqueous water-soluble ink solution. The water or the inksolution went up to the top of the collector in 10-20 seconds, whileuntreated collectors gave no ascent of water or the ink solution in thesame test as described above. The collectors obtained by the presentprocess were easily wetted with water and their contact angle of waterwas below 5.degree. On the other hand, the untreated collectors were notwetted with water when they were immersed in water and their contactangle of water was about 100.degree.

Writing Implement Example 2

[0264] 200 pieces of PP collector 2 were immersed in Impregnant B for 5minutes at 50° C. After this process, the same procedure as described inWriting Implement Example 1 was followed, except that methacrylic acidwas used as a monomer instead of acrylic acid. The obtained modified PPcollectors 2 gave a good wettability to water and their contact angle ofwater was below 5.degree. They were wetted well with water-soluble inksand gave the property preferable for ink collectors. On the other hand,the untreated PP collector 2 was not wetted with water when they wereimmersed in water and their contact angle of water was about 100.degree.

Writing Implement Example 3

[0265] ABS collector 1 and ABS collector 2 were used. Their impregnationprocess was carried out using Impregnant A at 20° C. After this process,the same procedure as described in EXAMPLE 1 FOR WRITING MATERIALS 1 wasfollowed. The grafting % of acrylic acid of the treated collectors was0.1-0.2%. Their wettablity to water or water-soluble inks was completelyimproved. Their contact angle of water was below 5.degree. The contactangle of untreated collectors to water was about 80-90.degree.

Writing Implement Example 4

[0266] The performance test of the PP collectors 1 obtained by themethod of Writing Implement Example 1 was carried out. A pen point 5made of polyester was connected to the hydrophilic PP collector 1 and anink tank chamber made of polypropylene was mounted on them. FIG. 1 givesthe structure in which a PP collector 1, an ink tank chamber 2 and a pencore 3 were set up.

[0267] In the collector1, the slit width between the farthest tooth ofthe comb from the pen nib is located at L1=3.5 cm, the slit widthbetween all teeth which are located over L2=2.7 cm is 0.15 mm, the slitwidth between all teeth located in the range of L2=2.7 cm and L3=2.2 cmis 0.22 mm and the slit width between all teeth located within L3=2.2 cmfrom the pen point is 0.25 mm. The portion between the collector 1 andthe ink tank chamber 2 was comparted by a barrier material which has alot of air-displacement voids whose size was smaller than any slitsbetween the teeth of the comb structure. The pen core 3 which ispenetrated to the collector dives further in the ink tank in adirect-liquid type pen. Then, the ink tank was filled with the ink 4which contains water as a main solvent and has a surface tension anddensity adjusted to be about 40 mnN/m and 1.08 g/ml at 25° C.,respectively. Thus, a direct-liquid type pen containing the ink 4 wasprepared.

[0268] When the nib 5 of the pen prepared in this way was orienteddownwardly, the outer pressure was gradually lowered and all of theslits in the teeth of the comb of the collector 4 were filled with theink 4. In the process that all of the slits in the teeth of the comb ofthe collector 4 were filled with the ink 4, any leak of the ink from thepen nib was not observed. In addition, the ink 4 stored in all of theslits in the teeth of the comb of the collector 4 did not leak from thepen nib 5, keeping the state of the ink retaining. After that, in thecourse that the outer pressure was gradually increased, all of the ink 4stored in the collector 1 returned to the ink tank 2. Thus, the inkcollector worked well as a temporary ink retaining body. Similarly tothe above manners, a hydrophilic ABS collector 1 which had been obtainedin Writing Implement Example 3 was mounted between a polypropylene-madeink tank chamber and a pen nib. When the writing test was carried out,this ink collector worked well.

Writing Implement Example 5

[0269] Using the hydrophilic ink collector 1 which had been prepared bythe same procedure as described in Writing Implement Example 1, an inkwhich contained ethyleneglycol monoether as a main solvent and has asurface tension and density adjusted to be about 38.5 mN/m and about1.03 g/ml at 25° C., respectively was filled in the ink tank by the samemanners as described in Writing Implement Example 4. Thus, adirect-liquid type writing pen filled with the ink was prepared.

[0270] The pen nib of the writing pen prepared in this way was orienteddownwardly and the outer pressure was gradually lowered and all of theslits in the teeth of the comb of the collector were filled with theink. In the process that all of the slits in the teeth of the comb ofthe collector were filled with the ink, any leak of the ink from the penpoint was not observed. In addition, the ink saved in all of the slitsin the teeth of the comb of the collector did not leak from the pen nib,keeping the state of the ink storing. After that, in the course that theouter pressure was gradually increased, all of the ink saved in thecollector returned to the ink tank. Thus, the ink collector worked wellas a temporary ink retaining body.

Writing Implement Example 6

[0271] A hydrophilic PP collector 2 obtained by the Modification 1 wasmounted between a PP-made ink tank chamber and a PET-made pen nib. Themechanism was similar to FIG. 1, but the collector structure was made bya stack of disks. In this collector with sheet bodies, the farthest diskfrom the pen point is located at L1=3.0 cm, the slit width between thesheet bodies which are located at over L2=2.5 cm is 0.20 mm, and theslit width between the sheet bodies which are located within L3=2.5 cmfrom the pen nib is 0.25 mm. The portion between the sheet bodies andthe ink tank chamber was comparted by a barrier material which has a lotof air-displacement voids whose size was smaller than any slits betweenthe disks. The pen core which is penetrated to the collector divesfurther in the ink tank in a direct-liquid type pen Then, the ink tankwas filled with the ink 4 which contains water as a main solvent and hasa surface tension and density adjusted to be about 35 mN/m and about1.08 g/ml at 25° C., respectively. Thus, a direct-liquid type pencontaining the ink was prepared. The direct-liquid type writing penprepared in this way gave no leak of ink when the outer pressure waschanged in the writing test and the ink collector worked well.

Writing Materials Example 7

[0272] An ABS collector made by sheet bodies obtained by the treatmentof Example 2 was mounted between a PP-made ink tank chamber and aPET-made pen point. In this collector, the farthest disk from the penpoint is located at L1=5.0 cm, and the distance of slits between allsheet bodies located in the range L2=4.0 cm is 0.10 mm, and the slitwidth between the sheet bodies which are located within L2-L3=4.0−3.5 cmfrom the pen nib is 0.15 mm, and the slit width between the sheet bodieswhich are located within L3=3.5 cm from the pen nib is 0.18 mm. Theportion between the collector and the ink tank chamber was comparted bya barrier material which has air-displacement voids whose size wassmaller than any slits between the sheet bodies. The pen core which ispenetrated to the collector dives further in the ink tank in adirect-liquid type pen. Then, the ink tank was filled with the ink whichcontained water as a main solvent and has a surface tension and densityadjusted to be about 35 mN/m and about 1.08 g/ml at 25° C.,respectively. Thus, a direct-liquid type writing pen containing the inkwas prepared. The direct-liquid type writing pen prepared in this waygave no leak of ink when the outer pressure was changed in the writingtest and the ink collector worked well as a temporary ink retainingbody.

Writing Implement Comparative Example 1

[0273] According to the same way as described in Writing ImplementExample 5, an untreated PP collector 1 was mounted between a PP-made inktank chamber and a PET-made pen nib and a direct-liquid type writing penwas prepared. In the course of storing the ink into the ink collector,when the pen nib of the writing pen was oriented downwardly and theouter pressure was gradually lowered, the ink leaked from the nib andthe collector did not work well.

Writing Implement Comparative Example 2

[0274] Using an untreated PP collector 2, the same test as described inWriting Implement

Comparative Example 1 was carried out. The ink leaked from the pen niband the collector did not work well. Writing Implement ComparativeExample 3

[0275] Using a PP collector 1 prepared by a well-known plasma treatment,the same test as described in Writing Implement Comparative Example 1was carried out. The ink leaked from the pen point and the collector didnot work well.

Writing Implement Comparative Example 4

[0276] Using an untreated ABS collector 2, the same test as described inWriting Implement Comparative Example 1 was carried out. The ink leakedfrom the pen point and the collector did not work well.

Writing Implement Example 8

[0277] Hydrophilic treatment of PP-Made Ink Tank by Modification Method1.

[0278] Ten PP-made ink tanks were immersed in 200 ml of an aqueousCarrier 2 (5 g) solution for 5 minutes at 70° C. in order to carry outthe impregnation step. Then, The treated specimens were centrifuged forone minute at a rotation rate of 1000 rpm. The impregnant seemed to becontained 2 wt. % in the treated specimens. Then, the specimens weretreated by a plasma treatment for 1 minute in order to carry out theactivation step. Then, the treated specimens were put in a Pyrexglass-made reaction vessel together with 120 ml of water, 10 mg of AIBNand 8 ml of methacrylic acid. After the reaction vessel was covered, theUV irradiation was made from the distance of 20 cm to the reactionvessel for two hours at 30° C. The treated ink tanks were taken out ofthe reaction vessel and washed with an aqueous detergent solution for 10minutes at 60° C. and washed with water and dried.

[0279] (Evaluation)

[0280] When water or water-soluble ink were put into the obtained inktank, the inner wall of the tank was wetted well by them. On the otherhand, the untreated ink tank was not wetted at all by water orwater-soluble ink, and when the untreated ink tank containing water orwater-soluble ink was shaken, water or water-soluble ink went out of thetank easily. The contact angle of water was 10-30.degree for the treatedink tanks and that for untreated PET-made ink tanks was averagely100.degree.

Writing Implement Example 9

[0281] Surface Treatment of a Pen Core and an Ink-Guiding Core byModification Method 2.

[0282] PET-made pen cores 1 (10 pieces), pen-cores 2 (10 pieces) andink-guiding cores (20 pieces) were immersed in 200 ml of Impregnant Afor 5 minutes at 20° C. in order to carry out the impregnation step.Then, the treated specimens were rinsed with methanol centrifuged fortwo minutes at a rotation rate of 1000 rpm. The impregnant seemed to becontained 4 wt. % in the treated specimens. Then, the UV irradiation wasmade to the specimens as the activation step. Then, the specimens weredipped in an aqueous CMC solution (concentration, 10 g/L) for one hourat 80° C. and then for two hours at 40° C. The pen cores and ink-guidingcores were taken out of the reaction mixture and washed with an aqueousdetergent solution for 10 minutes at boiling point, and washed withwater and dried. The water absorption test was carried out for thetreated specimens, untreated specimens and the specimens treated withsurfactants.

[0283] (Evaluation) Untreated specimens, the specimens made by thewell-known surfactant treatment and the specimens treated by the presentinvention were dipped in water for one minute, and the water absorbed inthe specimens were squeezed and the weight increase (water absorption %)was observed. In addition, the water absorption percentages foruntreated pen core 1, untreated pen core 2 and untreated ink-guidingcore were 27%, 43% and 21%, respectively. All of the results for thetreated specimens gave the improvement as follows; the water absorptionfor the treated pen core 1 was 176%, that for the treated pen core, 160%and that for the treated ink- guiding core, 61%, Actually, the pensassembled with the pen cores and ink- guiding cores treated by themethod of the present invention gave an excellent ink-guiding propertyin the real writing test.

Writing Implement Comparative Example 5

[0284] The evaluation test for the water absorption was carried out withthe pen cores and ink-guiding cores treated by surfactants. Although theinitial water absorption percentage of the materials treated bysurfactants was high, their water absorption property was decreasedrapidly when they were washed with water at 70° C. (a process that thesamples were washed with water for 5 minutes at about 70° C. with aliquor ratio of 1/100, rinsed with water and dried). Thus, thewell-known surfactant treatment seemed not to be available.

[0285] Pen cores 1 treated by a surfactant; initial water absorption 70%and water absorption after washing 27%.

[0286] Pen cores 2 treated by a surfactant; initial water absorption 43%and water absorption after washing 24%.

[0287] Ink-guiding cores treated by a surfactant; initial waterabsorption 56% and water absorption after washing 21%.

Writing Implement Example 10

[0288] Surface Treatment of Brush Heads for a Brush Pen by ModificationMethod 3 Brush heads 1 (10 pieces) and brush heads 2 (30 pieces) werewashed with methanol and dried. Then, the specimens were immersed in 200ml of Impregnant D for 5 minutes. Then, the treated specimens wererinsed with methanol and centrifuged for one minute at a rotation rateof 1000 rpm. The impregnant seemed to be contained 4 wt. % in thetreated specimens. Then the ozone treatment was made to the specimensfor 20 minutes. The formation of the carbonyl groups in the treatedspecimens was not observed well by IR spectroscopy. Then, the treatedbrush heads were dipped in an aqueous CMC solution (100 ml) for one hourat 80° C. Then, the specimens were washed with water at 60° C. Then, thetreated specimens were put in a reaction vessel containing water (120ml), acrylic acid (6 ml) and AIBN (80 mg), and the reaction vessel wassealed with a cover and allowed to stand for 2 hours at 80° C. Thespecimens were taken out of the reaction mixture and washed with anaqueous detergent solution for 10 minutes at 60° C., washed with waterand dried. The real water absorption test was carried out with thetreated materials, untreated materials and materials treated by thewell-known method with a surfactant.

[0289] (Evaluation) Untreated brush heads and the brush heads treated bythe present method were put on a surface of water, and the time when thespecimens were sunk in the water was observed. The material which iseasily wettable gives shorter time in this observation. The results wereas follows:

[0290] A brush head 1 (PBT resin-made): untreated materials=7 seconds08, the material treated by the present method=1 second 68,

[0291] A brush head 2 (nylon-made): untreated materials=11 seconds 05,the material treated by the present method=2 seconds 08,

[0292] The brush heads treated by the present method gave an excellentink-retaining property and an excellent durability as compared withuntreated ones or treated ones with a surfactant.

Writing Implement Comparative Example 11

[0293] Surface Treatment of PET Fiber Stuffing for Ink-Absorbing Use byModification Method 1

[0294] The PET fiber stuffing for the ink-retaining use (39.7 g) wastaken out of the tubes which holded it and washed sufficiently withwater at 50° C., rinsed with water and dried. After drying, the PETfiber stuffing gave no wettability. Then, the specimen was dipped in amixture of toluene (10 ml) with methanol (90 ml) for 5 minutes at 20° C.as the impregnation step. Then, the specimen was centrifuged for oneminute at a rotation rate of 1000 rpm. Then, the same procedure asdescribed in Writing Implement Example 1 was followed. The specimen wastaken out of the reaction mixture and washed with a boiling aqueousdetergent solution for 10 minutes, washed with water and dried. The realwater absorption test was carried out with the treated material,untreated material and material treated by a surfactant.

[0295] (Evaluation) Untreated material (whose surfactant contained wasremoved by washing) and the material treated by the present method wereput on a surface of water, and the time when the specimens were sunk inthe water was observed. The untreated material did not sink in the watereven after two hours. The material treated by the present methodabsorbed water and sank in the water in 15 seconds 31. The materialtreated by the present method gave really a good water soluble-inkretaining property.

Writing Implement Comparative Example 12

[0296] Treatment of Polyurethane-made Ink-Retaining Sponge byModification Method 3

[0297] The improvement of hydrophilic property of polyurethane-madeink-holding sponge was carried out by the same procedure as described inWriting Implement Example 10. The water absorption test was made by theobservation of the time when the specimens were sunk in the water. Thepolyurethane-made ink-retaining sponge treated by the present methodsank in the water in 7 seconds and 46. The untreated polyurethane-madeink-retaining sponge did not sink in the water even after two hours. Thewater absorption property of the treated specimen gave a durable waterabsorption property after 5 times washing with a detergent solution.

[0298] In addition, the use of each or mixture of Impregnants A, B, C, Dand F or Carriers 1 and 2 were effective for the hydrophilic treatmentsimilarly to the above result.

Writing Implement Comparative Materials 6

[0299] The polyurethane-made ink-retaining sponge treated by awell-known plasma treatment did not give a good water absorptionproperty and its durability as described above.

Writing Implement Comparative Example 7

[0300] The ink absorption property of the polyurethane-madeink-retaining sponge prepared by a well-known surfactant impregnationmethod was completely lost only by washing with water.

Writing Implement Example 13

[0301] Hydrophilic Treatment of Brush Heads 1 and 2 for a Brush Pen byModification Method 2

[0302] Brush heads 1 (10 pieces) and brush heads 2 (10 pieces) wereimmersed in 200 ml of Impregnant B for 5 minutes. Then, the liquidcontained in the treated specimens were removed by a centrifugeseparator. When the weight increase in the specimens treated with theimpregnant became to be 4 wt. % of the treated specimens, the ozonetreatment was made to the specimens for 30 minutes at 20° C. as theactivation step. Then, the treated specimens were put in a reactionvessel, in which a mixture of water (200 ml), KPS (60 mg), PVA (0.3 g)and methanol (6 ml) were added, and the reaction vessel was allowed tostand for 2 hours at 80° C. in order to carry out the hydrophilicpolymer treatment step. After the treatment, the specimens were washedwith water and an aqueous detergent solution and dried. The treatedspecimens gave the water absorption percentage, 500-600% and the weightincrease in the specimens by the present hydrophilic treatment was 0.1%.The water absorption percentage of the specimens was not changed bythree times of washing with an aqueous detergent solution.

[0303] (Evaluation) Untreated brush heads and the brush heads treated bythe present method were laid on a surface of water, and the time wherethe specimens sank in the water was observed. The results were asfollows:

[0304] A brush head 1 (PBT resin-made): untreated implements=7 seconds08, the implement treated by the present method=1 second 78,

[0305] A brush head 2 (nylon-made): untreated implements=11 seconds 05,the implement treated by the present method=3 seconds 43,

[0306] The brush heads treated by the present method gave an excellentink-retaining property and its durability when they were used for a realwriting test.

Writing Implement Example 14

[0307] Surface Treatment of PET Stuffing Fiber for Ink-absorbing Use byModification Method 1

[0308] The PET stuffing fiber for ink-retaining use (39.7 g) was washedsufficiently with water at 50° C., rinsed with water and dried. Afterdrying, the PET stuffing fiber gave no wettability. Then, the specimenwas dipped in a mixture of toluene (10 ml) with methanol (90 ml) for 5minutes at 20° C. as the impregnation process. Then, the liquidcontained in the treated specimens were removed for one minute by acentrifuge separator. The treated specimen seemed to contain theimpregnant of 4% of the weight. Then the specimens were treated by theozone treatment for 30 minutes. As the specimens were polyester, theobservation of carbonyl groups by IR spectroscopy was difficult. Then,the treated specimens were put in a reaction vessel, in which a mixtureof water (200 ml), KPS (60 mg), PVA (0.3 g) and methanol (6 ml) wereadded, and the reaction vessel was allowed to stand for 2 hours at 80°C. in order to carry out the hydrophilic polymer treatment step.

[0309] Then, as the grafting step, the treated specimens were put in aPyrex glass-made reaction vessel together with a mixture of water (120ml), methacrylic acid (5 ml) and AIBN (80 mg), and the reaction vesselwas sealed with a cover and was allowed to stand for 2 hours at 80° C.in order to carry out the thermal polymerization. After the treatment,the specimens were taken out of the vessel and washed with an aqueousdetergent solution for 10 minutes at 60° C. and water, and dried. Thus,the hydrophilic specimens were obtained. The real water absorption testwas carried out with the materials obtained in this way, the untreatedmaterials and the materials treated by a surfactant.

[0310] (Evaluation) Untreated material (of which surfactant was removedby washing) and the material treated by the present method were put on asurface of water, and the time when the specimens sank in the water wasobserved. The untreated material did not sink in the water even aftertwo hours. The material treated by the present method absorbed water andsank in the water in 12 seconds 1. In addition, the material treatedonly by a plasma treatment did not give an effective result. Thematerial treated by the present method gave really a good watersoluble-ink retaining property.

[0311] Examples and comparative examples for the battery separator useare described below.

Battery Separator Example 1

[0312] Treatment of PP/PE Non-woven Fabric (Sample 3) by ModificationMethod 1

[0313] The PP/PE non-woven fabrics (Sample 3) given in Table 1 wereimmersed in Impregnant A for 5 minutes at 20° C. in order to carry outthe impregnation step. Then, the collectors were rinsed with methanoland centrifuged for two minutes at a rate of 1000 rpm. The impregnantcontained in the specimens was about 2% in weight. Then, the specimenswere processed by a plasma treatment for 30 seconds as the activationstep. Then, the treated specimens were put in a cylindrical reactionvessel, and water (150 ml), potassium persulfate (100 mg) and acrylicacid and (10 ml) were put in the vessel. The UV irradiation was made tothe reaction vessel for two hours at 30° C. The obtained fabrics werewashed in a boiling aqueous solution of a detergent for 10 minutes andwashed with water and dried. The water absorption percentage of theuntreated fabrics was 5%, while that of the treated fabrics was 650%.The rate of water-absorption observed for the obtained fabrics was 7.0cm/ minute and that of the untreated fabrics was 0 cm/minute. Theresults of the evaluation of the chemical resistance of the obtainedfabrics required for the battery separator use are described below.

[0314] 1) Washing Fastness Test 1: the obtained specimens were examinedby Washing Fastness Test. After drying, the water absorption percentageof the specimens was 580%, the rate of water absorption was 6.5 cm,which gave a decrease of about 10%.

[0315] 2) Alkali-resistance Test: no decrease in the tensile strength ofthe obtained specimens was observed.

[0316] 3) Acid-resistance test: no decrease in the tensile strength ofthe obtained specimens was observed.

[0317] 4) Oxidant-resistance test: No decrease in the tensile strengthof the obtained specimens was observed.

Batteru Separator Comparative Example 1

[0318] An well-known nylon non-woven fabric for an alkali batteryseparator (FT-680N made by Japan Vilene Co. Ltd.) was prepared andexamined by the same test as described in Example for writingmaterials 1. 1) Alkali-resistance test: after washing with water anddrying, the water absorption percentage of the nylon separator decreasedto 70% of the original value. 2) Acid-resistance test: after drying, thewater absorption percentage of the nylon separator decreased to 60% ofthe original value. Its tensile strength decreased to 70% of theoriginal value. 3) Oxidant-resistance test: after drying, the waterabsorption percentage of the nylon separator decreased to 60% of theoriginal value. Its tensile strength decreased to 70% of the originalvalue.

Battery Separator Example 2

[0319] The same procedure as described in Battery Separator Example 1was followed, except that the PP non-woven fabric, Sample 1 in Table 1was used and except that the ozone treatment for 30 minutes at 20° C.was carried out as the activation step.

Battery Separator Example 3

[0320] Treatment of PP non-woven fabric 3 by Modification Method 3 andits application for the lead-storage battery.

[0321] Ten sheets (weight 22 g) of PP non-woven fabric 3 (Sample 7: size44 mm×145 mm) were immersed in Impregnant B for 5 minutes at 20° C. asthe impregnation step. Then, the UV irradiation was carried out to thespecimens for 20 minutes as the activation step (the distance betweenthe UV lamp and the specimens was 10 cm, and both surfaces of eachfabric were irradiated by IV). Then, the specimens were put in astainless-steel made reaction box, in which methanol (40 ml), water (500ml), PVA (8.0 g) and AIBN (40 mg) were put and the reaction mixture wasallowed to stand for one hour at 80° C. After the treatment, thespecimens were washed sufficiently with water at 60° C. Then, in orderto carry out the grafting step, the specimens were put in a reactionvessel, in which methanol (20 ml), CAN (20 mg), water (500 ml) andacrylic acid (20 ml) were put, and the reaction mixture was allowed tostand for two hours at 70° C. The obtained fabrics were washed with aboiling soap (sodium salt of fatty acid) solution for 5 minutes andwashed sufficiently with water and dried. The weight increase in thefabrics by the grafting was 4%. The water absorption obtained by thewater absorption test for the treated fabrics was 770% and the tensilestrength of the treated fabrics was 1.6 kg. The tensile strength of theuntreated fabric corresponding to that used here was 1.68 kg. Thechemical resistance of the fabrics necessary for the battery separatoruse was evaluated as follows. 1) Alkali-resistance test: the tensilestrength of the obtained treated fabric was 1.42 kg. 2) Sulfuricacid-resistance test: the tensile strength of the obtained treatedfabric was 1.42 kg. 3) Oxidant-resistance test: after drying, the waterabsorption of obtained treated fabric was 770%. Its tensile strength was1.42 kg. The specimens treated by the present method gave good resultsin an absorption property of electrolytic solution, an acid-resistance,an oxidant-resistance and an alkali-resistance. They were preferable forthe battery separator.

Battery Separator Comparative Example 2

[0322] A PP/PE non-woven fabric which was treated by the well-knownhydrophilic treatment with a surfactant (the fabric FT-310 made by JapanVilene Co. Ltd. impregnated with surfactants; the unit weight wassimilar to that of PP non-woven fabric in Table 1) was prepared and usedas a battery separator. The results for the evaluation examined by thesame test as described in Example for battery separators 1 are asfollows. 1) Alkali-resistance test: after washing with water and drying,the water absorption percentage of the separator decreased to 10% of theoriginal value. 2) Acid-resistance test: after sufficient washing withwater and drying, the water absorption percentage of the separatordecreased to 5% of the original value. 3) Oxidant-resistance test: afterdrying, the water absorption percentage of the separator decreased to 5%of the original value. Its tensile strength decreased to 40% of theoriginal value.

Battery Separator Example 4

[0323] Treatment of PP non-woven fabric 1 by Modification Method 2

[0324] The PP non-woven fabric 1 (weight 67.5 g and size 27cm×500cm),Sample 1 in Table 1 was immersed in 500 ml of Impregnant A for 10minutes at 50° C. as the impregnation step. The specimen was centrifugedin the same procedure as Example for battery separator 1. Then, thespecimen was made by the ozone treatment for 30 minutes. Then, thetreated fabric was put in an Erlenmeyer flask, and methanol (200 ml),water (500 ml), PVA (6.25 g) and potassium persulfate (1.14 g) were putin the flask. The flask was allowed to stand for two hours at 80° C.After this process, the specimen was washed with a water for 10 minutesat 60° C., a boiling aqueous detergent solution and washed with water,and dried. The water absorption obtained by the water absorption testfor the treated specimen was 180% and the water absorption rate was 3.5cm/minute. That of the untreated fabric corresponding to the treatedspecimen was 0 cm/minute. In the alkali-resistance test, theacid-resistance test and the oxidant-resistance test, the decrease inthe tensile strength of the obtained treated specimen was not observed.

Battery Separator Example 5

[0325] Treatment of PP Non-woven Fabric 2 by Modification Method 3 andits Application for the Alkali Battery and its Performance Evaluation

[0326] The PP non-woven fabric 2 (weight 63 g), Sample 2 in Table 1 (size 18 cm×500 cm) was immersed in 1L of Impregnant D for 20 minutes at40° C. as the impregnation step. Then, the specimen was centrifuged atrotation rate of 1000 rpm and the weight increase in the specimen causedby the impregnation step was about 4%. The specimen was exposed to ozonefor 20 minutes as the activation step. Then, as the hydrophilic polymertreatment step, the specimen was treated with an aqueous solution (500ml) of CMC (6.5 g) and KPS (0.5 g) four 2 hours at 80° C. The specimenwas washed with water. Then, the specimen was put in a mixture of water(500 ml), CAN (0.5 g) and acrylic acid (50 ml) four two hours at 80° C.The obtained specimen was washed with a water for 10 minutes at 60° C.,a boiling aqueous detergent solution and washed with water, and dried.The water absorption obtained by the water absorption test for thetreated fabric was 160% and the water absorption rate was 4.0 cm/min.The water absorption of the untreated fabric was 40% and its waterabsorption rate was 0 cm/min. In order to see the battery separatorusage, the following tests were examined. The obtained specimen did notgive a decrease in water absorption percentage and a decrease in tensilestrength in the alkali-resistance test, the acid-resistance test and theoxidant-resistance test. In the washing test of the obtained specimen,no decrease was observed in the water absorption percentage, the waterabsorption rate and the water retaining property.

Battery Separator Example 6

[0327] Preparation of Lead Storage Battery Separator by the Treatment ofGlass Fiber/PP of Sample 8 by the Modification Method 2

[0328] The same procedure as Example for battery separator 4 wasfollowed, except that the specimen of Sample 8 was used and except thatthe Impregnant B was used for the impregnation step.

Battery Separator Example 7

[0329] Preparation of Lead Storage Battery Separator by the Treatment ofPP Non-woven

[0330] Fabric 3 by the Modification Method 1

[0331] The of PP non-woven fabric 3 (weight 520 g), Sample 7 in Table 1(size 77 mm×5 m) was used and its impregnation process was carried outin the same procedure as Example for battery separator 1. As theactivation process, the specimen was exposed to ozone for 30 minutes.Then, the specimen was put in a cylindrical reaction vessel, andmethanol (30 ml), AIBN (100 mg) and acrylic acid (20 ml) were added inthe vessel. The thermal grafting was carried out at nitrogen atmosphereby allowing to stand it for 3 hours at 80° C. Basic experimentalprocedures were similar to those in Example for battery separator1. Theweight increase in the specimen by grafting was 4%. The chemicalresistance of the specimen necessary for the battery separator use wasevaluated as follows. The obtained specimen did not give a decrease inwater absorption percentage and a decrease in tensile strength in thealkali-resistance test and the acid-resistance test. Theoxidant-resistance test: after sufficient washing and drying, the waterabsorption of the specimen was 470%. Its tensile strength was 1.47 kg.These values were not changed before and after the test.

Battery Separator Example 8

[0332] Processing of Sample 17 by Modification Method 3.

[0333] A porous PE film (Sample 17) was immersed in Impregnant E as theimpregnation treatment for 10 minutes at 50° C. The specimen was treatedby a plasma treatment for 30 seconds. As the polymer treatment step, thespecimen was dipped in an aqueous PVA solution for one hour. Thegrafting to the specimen was carried out with CAN and acrylic acid bythe UV irradiation for one hour at 30° C. The washing method and theevaluation of the performance were made by the same way as described inExample for battery separator 3. The obtained specimen gave theexcellent property in a water absorption, a tensile strength and analkali-resistance.

Battery Separator Example 9

[0334] Evaluation Test 1 for Alkali Battery Separator

[0335] A Ni-Cd battery (a nominal capacity: 4Ah) was made using thehydrophilic PP non-woven fabric prepared in Example for batteryseparator 2 as a battery separator. Similarly to this, batteries usingthe non-woven fabrics for battery separators obtained in ComparativeExamples 1 and 2 were prepared. The charge curves for these batteriesexamined by a repeated overcharge at 60° C. are given in FIG. 2. Theinner resistance of the battery incorporated with the non-woven fabricof the present invention was observed to be smaller than the materialsobtained by Battery Separator Examples 1 and 2. In addition, thecharge/discharge performance of the battery with the separator preparedby the present invention at high temperature was more excellent thanthat with the surfactant-impregnated polypropylene non-woven fabricprepared in Battery Separator Comparative Example 2. Besides, thisproperty was not changed after the charge/discharge repeated five times.The separator of the present invention detached from the battery gave anexcellent electrolyte absorption property (electrolytic solutionabsorption: 655%), but that of the surfactant impregnated PP/PEnon-woven fabric of Battery Separator

Comparative Example 2 gave a decrease (electrolytic solution absorption:10%). In addition, it is well known that a nylon non-woven fabric ofBattery Separator Comparative Example 1 cannot bear a long-time use.Battery Separator Example 10

[0336] Evaluation Test for the Performance of Alkali Battery Separators2

[0337] The evaluation test for the performance of alkali batteryseparators was carried out for the materials of Battery SeparatorExamples 1 and 3 and Battery Separator Comparative Example 2. Treatedspecimens were incorporated in a sealed nickel-hydrogen battery of acoin-size (a nominal capacity: 500 mAh), and nine batteries wereprepared. When the property of the batteries looked stable, they werecharged to 120% of the capacity by an electric source of 0.1 C(Coulomb). After four cycles of charge-discharge processes, thepercentage of an average value of a residual capacity (C) to theoriginal value for each of batteries was estimated after two weeks at45° C. The observed values are listed in Table 3. In order to use as apreferable alkali battery separator, the hydrophilic treated materialneeds the excellent property in the electrolytic solution absorption,the alkali-resistance, the acid-resistance and the charge-dischargeperformance. As the Battery Separator Examples 1 an 2 gave an excellentelectrolytic solution absorption, they are preferable for the alkalibattery separators. On the other hand, the well-knownsurfactant-containing PP/PE non-woven fabrics gave a low electrolyticsolution absorption.

Battery Separator Comparative Example 3

[0338] Durability Test of Water Absorption Property of Sample 8

[0339] Sample 8 in Table 1 is a material which is composed of glassfibers (average diameter 20 microns) bonded simply by meltingpolyethylene fiber (average diameter 1-2 microns) and solidified by awater-soluble adhesive. As a fact, this material is used for the leadstorage batteries. This material gave a water absorption of 730%. Whenone sheet of Sample 8 (size 77 mm×145 mm, weight 2.64 g) was dipped in500 ml of boiling water for 5 minutes, the fibers of the material wereraveled out. Thus, it was impossible to use this material.

Battery Separator Comparative Example 4

[0340] Grafting of acrylic acid to PP/PE non-woven fabric by well-knownUV irradiation

[0341] PP/PE non-woven fabric (weight 1.2 g), Sample 3 in Table 1 (size7.7 cm×10 cm) was put in a reaction vessel containing acrylic acidmonomer 20.0%, water 78.8%, benzophenone 0.2% and methanol 1.0% (each %represents weight %), and the reaction mixture was exposed by the UVirradiation for 60 minutes. After the reaction, the product was jelledwith resulted polymers, but when the product was washed with a boilingaqueous soap solution for 10 minutes and washed with water, the polymerswere dissolved in the washing process. The water absorption percentageof the treated non-woven fabric was 100% (that of the untreatednon-woven fabric was 48%). Its grafting percentage was 1%. Namely, thewell-known grafting method by the UV irradiation gave a large apparentgrafting %, but the homopolymer of acrylic acid was removed from thefabric by the dissolution by washing with boiling water. The obtainedspecimen here was not suitable for a battery separator use, because theproperty of retaining electrolytic solutions was low and its durabilitywas not preferable.

Comparative Example for Battery Separator 5

[0342] Glass fiber separater

[0343] A separator of glass fiber non-woven fabric with an acidresistance which is extensively used for a sealed-type lead storagebattery was examined. This separator is impregnated with a surfactant toget a good wettablity at the initial stage. The separator is 1.0 mmthick, unit weight 342 g/m2, apparent density 0.20 g/c m³, fiberdiameter 10 microns, fiber length 4-8 cm, volume of vacancy 93%; it gavea water absorption of 780%.

Battery Separator Example 11

[0344] Evaluation test for the performance of a separator forlead-storage batteries

[0345] Sealed-type lead storage batteries which were incorporated withseparators prepared in Battery Separator Examples 6 and 7 or a glassfiber battery separator prepared in Battery Separator ComparativeExample 5 were made as a test. The sealed-type lead storage battery gavea voltage 4 V and a capacity 3.8 Ah. As a discharge test, the time whenthe final voltage indicated 2.8 V at a discharge current 13 A wasobserved. Charge-discharge tests were repeated and the result of theelectrical property were listed in Table 4. In addition, the separatorsfor the lead storage battery prepared in Battery Separator Examples 6and 7 gave a more excellent durability.

[0346] As described in the above results, the lead storage battery usedwith the hydrophilic polyolefin non-woven fabric prepared by the methodof the present invention gave more excellent property in aliquid-retaining, a longer life-time and a lightweight than theconventional lead storage battery.

Industrial Applicability

[0347] As described above, various polymeric materials improved by thepresent invention gave an excellent water absorption property and a goodadhesion property with adhesives without the decrease in strength.Besides, the property obtained by this modification gave an excellentdurability. In addition, the polyolefin filter of which hydrophilicproperty was modified by the present invention gave a development of theuse in the filtration of aqueous solutions. As the material improved bythe present invention gives a water absorption property and an excellentadhesion property to synthetic papers, the improvement of printingproperty of them is also expected. As the adhesion property of manykinds of polymeric materials containing carbon fibers is extremelyimproved, hydrophilic materials available for reinforcing fibers forcomposite materials can be obtained by the present invention. As thehydrophilic property of various kinds of polymeric materials can beimproved by the present invention, the present invention can be usefulto improve the property of various kinds of medical, sanitary, orcosmetic supplies and textile products for clothing, an adhesionproperty of orthodontic brackets made of polymers and the wettability towater for the medical supplies or instruments.

[0348] Although the kind of polymers useful for the production of themembers for writing implements such as marker pens, fountain pens, brushpens, and so forth has been limited, the prevent invention can enable touse many kinds of polymers containing polyolefins such as polypropylene,polyethylene, and so forth of which modification is considered to bedifficult for the production of the writing implements. The preventinvention can give the materials having the property of a safety, anacid-resistance and an alkali-resistance, which was not seen so far.

[0349] In addition, the present invention can provide battery separatorswhich have the excellent property in an absorption property ofelectrolytic solutions, an acid-resistance, an alkali-resistance and aphysical strength, easily and with a cheap price. In addition, thebatteries produced by using the separators prepared by the method of thepresent invention do not lose the excellent property for a long period.TABLE 1 Tensile Thick- Unit Fiber Strength Fiber Main ness weightdiamete kg/15 mm length Density Voids Production Sample Name material μmg/m² μm width cm g/cm³ % method 1 PP non- PP 150 50 12.5 5.35 Continuing0.33 63 Spun bond woven fabric1 2 PP non- PP 210 45 12.5 1.8 ContinuingMelt blow woven fabric2 3 PP/PE non- PP/PE 300 76 6.2 8.03 3-6 0.25 72Heat set woven fabric water slip 4 PET non- PET 380 57 12.5 ContinuingMelt blow woven fabric 5 PP plain PP 120 150 20 1.21 1   Warp 40/cmfabric Weft 30/cm 6 PP/PET non- PP/PET 150 27 3.6 5.1 Spun bond wovenfabric 7 PP non- PP 1000 200 12.5 1.45 1   0.2 78 Spun bond wovenfabric3 8 Glass fiber/ Glass fiber/ 1000 213 201-2 1.68 1-5 0.39 Heatfusing PE PE fiber 9 Carbon fiber Carbon 150 50 1.4 Continuing 0.2Acrylic fiber fiber bundle raw material 10 Wool fiber Wool 500 188 8.88fabric 11 PP film PP 20 17 2.39 Spun bond 12 PET fiIm PET 60 72 11.6Spun bond 13 HMPE plate Super high 700 467 Average-Mwt Mwt Pe 6 billion14 PP synthetic PP 130 92 17.9 White with paper air bubbles 15 Porous PESuper high 60 30 1.97 Average-Mwt 5 billion film Mwt PE Average voidsize = 1 μm 16 Porous PSU PSU 170 50 0.91 Average void size = 2 μm film17 Porous PE Super high 15 7.7 Average-Mwt 5 billion film Mwt PE Averagevoid size = 60 nm

[0350] TABLE 2 Impregnant process Activation process Grafting PolymericTemp. Time Temp. Time Temp. Time Example material Impregnant ° C. min.Method ° C. min. Method Monomer ° C. min. Example1 PPn.w.f.l A 50 10 OZ20 30 UV/CAN AA 30 2 Example2 PPn.w.f.l B 50 10 PL 20 0.5 UV/CAN MA 30 2Example3 PPn.w.f.l F 50 10 UV 30 60 UV/CAN AA 30 2 C. Exam. 1 PPn.w.f.lC. Exam. 2 PPn.w.f.l OZ 30 30 UV/CAN AA 30 2 C. Exam. 3 PPn.w.f.l UV/CANAA 30 2 C. Exam. 4 PPn.w.f.l OZ 30 30 C. Exam. 5 PPn.w.f.l A 50 10UV/CAN AA 30 2 Example4 PP Plain c. C 50 10 PL 30 0.5 UV/CAN AA 30 2 C.Exam. 6 PP Plain c. C. Exam. 7 PP Plain c. PL 30 0.5 Example5 PETn.w.f.Carrier2 50 12 OZ 20 30 Heat/AIBN AA 80 2 Example6 PETn.w.f. A 30 5 OZ20 30 UV MMA 30 2 C. Exam. 8 PETn.w.f. C. Exam. 9 PETn.w.f. OZ 20 30UV/CAN AA 30 2 C. Exam. 10 PETn.w.f. UV/CAN AA 30 4 C. Exam. 11PETn.w.f. OZ 20 30 C. Exam. 12 PETn.w.f. A 30 5 Example7 P/E n.w.f. C 5010 PL 30 0.5 CAN MA 80 2 Example8 P/E n.w.f. E 50 10 PL 30 0.5 KPS AA 302 C. Exam. 13 P/E n.w.f. Example9 PET film E 70 15 OZ 20 30 UV AA 30 2C. Exam. 14 PET film C. Exam. 15 PET film OZ 20 30 UV AA 30 2 C. Exam.16 PET film UV/CAN AA 30 2 C. Exam. 17 PET film OZ 20 45 C. Exam. 18 PETfilm E 70 15 UV AA 30 2 Example10 HMPE plate B 70 15 OZ 20 45 UV/CAN AA30 2 C. Exam. 19 HMPE plate C. Exam. 20 HMPE plate OZ 20 45 UV/CAN AA 302 C. Exam. 21 HMPE plate UV/AIBN AA 30 2 C. Exam. 22 HMPE plate OZ 20 45C. Exam. 23 HMPE plate A 70 15 OZ 20 45 UV/AIBN AA 30 2 Example11 PPfilm C 70 15 PL 30 0.5 UV/AIBN AA 30 2 C. Exam. 24 PP film C. Exam. 25PP film PL 30 0.5 UV/AIBN AA 30 2 C. Exam. 26 PP film UV/AIBN AA 30 2 C.Exam. 27 PP film PL 30 0.5 C. Exam. 28 PP film A 70 15 UV/AIBN AA 30 2Water Water Water Peel- Polymeric absorption absption absption strengthContact Example material 1% rate mm/min. 3% of adhesion angle ° Example1PPn.w.f.l 310 20 305 Example2 PPn.w.f.l 300 18 290 Example3 PPn.w.f.l300 20 298 C. Exam. 1 PPn.w.f.l 5 0 5 C. Exam. 2 PPn.w.f.l 80 0 60 C.Exam. 3 PPn.w.f.l 80 0 60 C. Exam. 4 PPn.w.f.l 8 0 6 C. Exam. 5PPn.w.f.l 70 0 50 Example4 PP Plain c. 320 15 310 C. Exam. 6 PP Plain c.2 0 2 C. Exam. 7 PP Plain c. 80 0 60 Example5 PETn.w.f. 1100 18 1000Example6 PETn.w.f. C. Exam. 8 PETn.w.f. 100 0 100 C. Exam. 9 PETn.w.f.400 5 350 C. Exam. 10 PETn.w.f. 320 3 290 C. Exam. 11 PETn.w.f. 110 0110 C. Exam. 12 PETn.w.f. 300 4 240 Example7 P/E n.w.f. 800 18 780Example8 P/E n.w.f. 750 20 720 C. Exam. 13 P/E n.w.f. 5 0 5 Example9 PETfilm 63 90 4 C. Exam. 14 PET film 85 9 1 C. Exam. 15 PET film 75 60 1.71C. Exam. 16 PET film 80 68 1.41 C. Exam. 17 PET film 71 64 1.5 C. Exam.18 PET film 81 10 1.71 Example10 HMPE plate 76 220 167 C. Exam. 19 HMPEplate 105 3 1 C. Exam. 20 HMPE plate 81 18 1.3 C. Exam. 21 HMPE plate 905 1.2 C. Exam. 22 HMPE plate 91 6 1.1 C. Exam. 23 HMPE plate 92 10 1.3Example11 PP film 86 280 33 C. Exam. 24 PP film 100 20 1 C. Exam. 25 PPfilm 91 181 21 C. Exam. 26 PP film 95 80 13 C. Exam. 27 PP film 95 202.7 C. Exam. 28 PP film 96 20 15

[0351] TABLE 3 Retention of Retention of Alkali-resi Capacityelectrolytic electrolytic stance after Solution at a solution (Decreaseself- initial stage after the in weight dischar Examples (%) test (%)(%)) ge (%) Separator 201 190 0.1 90 Example 1 Separator 160 160 0.1 91Example 2 Separator Comparative 400 20 3 65 Example 2

[0352] TABLE 4 Separator Separator Separator Comparative Item Example 6Example 7 Example 5 Hydrophilic Sample 8 Sample 7 Acid-resistancematerial Glass fiber/PP PP Glass fiber Electric 0.009 0.0007 0.0009resistance (ohm dm²/cell) Discharge  218 minutes  241 minutes  240minutes capacity at five hours high rate  118 seconds  132 seconds  130seconds Discharge capacity At low temperature Voltage at 1.62 V 1.58 V1.57 V 5 seconds Initial water  7.0 cm/minute  5.0 cm/minute  7.2cm/minute absorption rate Water  6.5 cm/minute  5.0 cm/minute  4.8cm/minute absorption rate after 3 months Initial water 774% 643% 780%retension Water 740% 640% 460% retention after 3 months

What is claimed is:
 1. A method of modifying the surface of a polymericmaterial which comprises: (1) subjecting the polymeric material to animpregnation step to contact the polymeric material with a single or amixture of compounds having an impregnation property to the polymericmaterial in the manner so that the content of the impregnated compoundin the layer within the depth of 100 micron from the surface of thepolymeric material is in the range of 0.1% to 40% by weight of thetreated polymeric material without any substantial deformation of thepolymeric material; (2) subjecting the polymeric material produced insaid impregnation step to an activation step to introduce carbonylgroups into the polymeric material; and (3) conducting a step of monomergrafting to the polymeric material produced in said impregnation stepand subsequent said activation step.
 2. A method of modifying thesurface of a polymeric material which comprises: (1) subjecting thepolymeric material to an impregnation step to contact the polymericmaterial with a single or a mixture of compounds having an impregnationproperty to the polymeric material in the manner so that the content ofthe impregnated compound in the layer within the depth of 100 micronfrom the surface of the polymeric material is in the range of 0.1% to40% by weight of the treated polymeric material without any substantialdeformation of the polymeric material; (2) subjecting the polymericmaterial produced in said impregnation step to an activation step tointroduce carbonyl groups into the polymeric material; and (3)subjecting the polymeric material produced in said impregnation step andsubsequent said activation step to a step of treatment with hydrophilicpolymers,
 3. A method of modifying the surface of a polymeric materialwhich comprises: (1) subjecting the polymeric material to animpregnation step to contact the polymeric material with a single or amixture of compounds having an impregnation property to impregnate thepolymeric material in the manner so that the amount of the impregnatedcompound in the layer within the depth of 100 micron from the surface ofthe polymeric material is in the range of 0.1% to 40% by weight of thepolymeric material without any substantial deformation of the polymericmaterial; (2) subjecting the polymeric material produced in saidimpregnation step to an activation step to introduce carbonyl groupsinto the polymeric material; (3) subjecting the polymeric materialproduced in said impregnation step and subsequent said activation stepto a step of treatment with hydrophilic polymers, and (4) conducting astep of monomer grafting to the polymeric material produced in saidimpregnation step, subsequent said activation step and subsequent saidstep of treatment with hydrophilic polymers.
 4. The method according toany one of claims 1 to 3, wherein said polymeric materials are in theform of any one of fibers, woven fabrics, knitted webs, non-wovenfabrics, boards, rods, films, sheets, porous films, and members orproducts of molded materials in a given shape or composite materialswith the other materials.
 5. The method according to any one of claims 1to 3, wherein said polymeric materials contain at least one or morekinds of anti-oxidants or stabilizers.
 6. The method according to anyone of claims 1 to 3, wherein said impregnation step is conducted at atemperature below the melting point or the softening point of thepolymeric materials.
 7. The method according to any one of claims 1 to3, wherein said activation step is conducted by at least one treatmentsselected from the group consisting of an ozone treatment, a plasmatreatment, a UV irradiation treatment and a high voltage electricdischarge treatment.
 8. The method according to claim 1 or claim 3,wherein said monomer is a compounds having a carbon-carbon double bond.9. The method according to claim 1 or claim 3, wherein said monomer isat least one monomer selected from the group consisting of acrylic acid,methacrylic acid, vinyl acetate, 2-butene acid, ethylene sulfonic acid,hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acryl amide, vinylpyridine, vinyl pyrrolidone, vinyl carbazole, maleic anhydride andpyromellitic dianhydride.
 10. The method according to claim 2 or claim3, wherein said hydrophilic polymer is at least one of the polymersselected from the group consisting of polyvinyl alcohol, carboxymethylcellulose, polyhydroxy ethylmethacrylate, poly-α-hydroxy vinylalcohol,polyacrylic acid, polyvinyl pyrrolidone, polyalkylene glycols, starch,glucomannan, silk fibroin, sericin, agar, egg white and sodium arginate.11. The method according to claim 1 or claim 3, wherein said step ofmonomer grafting is carried out by at least any one of or more of thefollowing three methods: (1) in the presence of catalysts or initiators,(2) heating in the presence or absence of catalysts or initiators, and(3) UV irradiation in the presence or absence of catalysts, initiatorsor photo-sensitizers.
 12. The method according to claim 2 or claim 3,wherein said treatment with a hydrophilic polymer is carried out in thepresence of catalysts or initiators.
 13. The method according to claim11 or claim 12, wherein said initiators are at least one compoundsselected from the group consisting of peroxides, cerium ammonium nitrate(IV), persulfates, oxidation-reduction catalysts and the otherinitiators for radical polymerization.
 14. Polymeric material obtainedby the modification method according to any one of claims 1 to
 13. 15.Wiping/cleansing materials, materials for filters, water absorptionmaterials, water retention materials, synthetic papers,medical/sanitary/cosmetic supplies, materials for medical supplies orinstruments, and materials for microorganism culture media containingmodified polymeric materials obtained by the modification methodaccording to any one of claims 1 to
 13. 16. Writing materials containingmodified polymeric materials obtained by the modification methodaccording to any one of claims 1 to
 13. 17. Writing implementscontaining at least one writing materials described in claim
 16. 18.Dentition orthodontic appliances containing modified polymeric materialsobtained by the modification method according to any one of claims 1 to13.
 19. Dentition orthodontic appliances containing modified polymericmaterials obtained by the methods which comprises: (1) subjecting thepolymeric materials to an activation step to introduce carbonyl groupsto the polymeric materials; and (2) conducting a step of monomergrafting to the polymeric materials produced by said activation step.20. Battery separators containing modified polymeric materials obtainedby the modification method according to any one of claims 1 to 13 andbatteries in which said battery separators are used.